CN1333059C - Spiro-compound used as perfume component - Google Patents
Spiro-compound used as perfume component Download PDFInfo
- Publication number
- CN1333059C CN1333059C CNB2003101003808A CN200310100380A CN1333059C CN 1333059 C CN1333059 C CN 1333059C CN B2003101003808 A CNB2003101003808 A CN B2003101003808A CN 200310100380 A CN200310100380 A CN 200310100380A CN 1333059 C CN1333059 C CN 1333059C
- Authority
- CN
- China
- Prior art keywords
- spiral shell
- alkene
- carbon
- ketone
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002304 perfume Substances 0.000 title claims description 25
- 150000003413 spiro compounds Chemical class 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 199
- 150000001875 compounds Chemical class 0.000 claims abstract description 133
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 122
- 235000019439 ethyl acetate Nutrition 0.000 claims description 41
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 40
- 235000013599 spices Nutrition 0.000 claims description 26
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 22
- 239000003205 fragrance Substances 0.000 claims description 19
- 239000011159 matrix material Substances 0.000 claims description 15
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 12
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 5
- 239000004753 textile Substances 0.000 claims description 5
- 241000195940 Bryophyta Species 0.000 claims description 2
- 239000002386 air freshener Substances 0.000 claims description 2
- 230000001166 anti-perspirative effect Effects 0.000 claims description 2
- 239000003213 antiperspirant Substances 0.000 claims description 2
- 239000002537 cosmetic Substances 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- 230000036541 health Effects 0.000 claims description 2
- 238000010409 ironing Methods 0.000 claims description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 235000011929 mousse Nutrition 0.000 claims description 2
- 235000019198 oils Nutrition 0.000 claims description 2
- 239000002453 shampoo Substances 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 229940125782 compound 2 Drugs 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 36
- 150000002576 ketones Chemical class 0.000 abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 25
- 150000002148 esters Chemical class 0.000 abstract description 9
- 125000003118 aryl group Chemical group 0.000 abstract description 7
- 239000004615 ingredient Substances 0.000 abstract description 7
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 239000004480 active ingredient Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 230000035943 smell Effects 0.000 description 35
- 239000002585 base Substances 0.000 description 29
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 29
- 239000000047 product Substances 0.000 description 27
- 239000012043 crude product Substances 0.000 description 26
- 238000000526 short-path distillation Methods 0.000 description 26
- 239000002904 solvent Substances 0.000 description 26
- 238000007429 general method Methods 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 239000000341 volatile oil Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 12
- 241000723346 Cinnamomum camphora Species 0.000 description 12
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 12
- 229930008380 camphor Natural products 0.000 description 12
- 229960000846 camphor Drugs 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 238000006352 cycloaddition reaction Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 229910010082 LiAlH Inorganic materials 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 238000005698 Diels-Alder reaction Methods 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000000796 flavoring agent Substances 0.000 description 8
- 235000019634 flavors Nutrition 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 240000004510 Agastache rugosa Species 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- -1 methylidene, ethyl Chemical group 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- ZMPHKSUOIYSSOS-UHFFFAOYSA-N 2-ethylidene-4,4-dimethylcyclohexan-1-one Chemical compound CC=C1CC(C)(C)CCC1=O ZMPHKSUOIYSSOS-UHFFFAOYSA-N 0.000 description 6
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 244000050510 Cunninghamia lanceolata Species 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- DXASQZJWWGZNSF-UHFFFAOYSA-N n,n-dimethylmethanamine;sulfur trioxide Chemical group CN(C)C.O=S(=O)=O DXASQZJWWGZNSF-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 5
- 206010013911 Dysgeusia Diseases 0.000 description 5
- 244000004281 Eucalyptus maculata Species 0.000 description 5
- UAVFEMBKDRODDE-UHFFFAOYSA-N Vetiveryl acetate Chemical compound CC1CC(OC(C)=O)C=C(C)C2CC(=C(C)C)CC12 UAVFEMBKDRODDE-UHFFFAOYSA-N 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 239000001724 (4,8-dimethyl-2-propan-2-ylidene-3,3a,4,5,6,8a-hexahydro-1H-azulen-6-yl) acetate Substances 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 235000005794 Salvia japonica Nutrition 0.000 description 4
- 244000295490 Salvia japonica Species 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- UWKAYLJWKGQEPM-LBPRGKRZSA-N linalyl acetate Chemical compound CC(C)=CCC[C@](C)(C=C)OC(C)=O UWKAYLJWKGQEPM-LBPRGKRZSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000008786 sensory perception of smell Effects 0.000 description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- DNRJTBAOUJJKDY-UHFFFAOYSA-N 2-Acetyl-3,5,5,6,8,8-hexamethyl-5,6,7,8- tetrahydronaphthalene Chemical compound CC(=O)C1=C(C)C=C2C(C)(C)C(C)CC(C)(C)C2=C1 DNRJTBAOUJJKDY-UHFFFAOYSA-N 0.000 description 3
- RBBXMNMQOGQFMV-UHFFFAOYSA-N 2-propylidenecyclopentan-1-one Chemical compound CCC=C1CCCC1=O RBBXMNMQOGQFMV-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000349731 Afzelia bipindensis Species 0.000 description 3
- 244000153234 Hibiscus abelmoschus Species 0.000 description 3
- 244000178870 Lavandula angustifolia Species 0.000 description 3
- 235000010663 Lavandula angustifolia Nutrition 0.000 description 3
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 3
- 241000018646 Pinus brutia Species 0.000 description 3
- 235000011613 Pinus brutia Nutrition 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000001102 lavandula vera Substances 0.000 description 3
- 235000018219 lavender Nutrition 0.000 description 3
- MQWCXKGKQLNYQG-UHFFFAOYSA-N methyl cyclohexan-4-ol Natural products CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 3
- KVWWIYGFBYDJQC-UHFFFAOYSA-N methyl dihydrojasmonate Chemical compound CCCCCC1C(CC(=O)OC)CCC1=O KVWWIYGFBYDJQC-UHFFFAOYSA-N 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- YBUIAJZFOGJGLJ-SWRJLBSHSA-N 1-cedr-8-en-9-ylethanone Chemical compound C1[C@]23[C@H](C)CC[C@H]3C(C)(C)[C@@H]1C(C)=C(C(C)=O)C2 YBUIAJZFOGJGLJ-SWRJLBSHSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- BGTBFNDXYDYBEY-FNORWQNLSA-N 4-(2,6,6-Trimethylcyclohex-1-enyl)but-2-en-4-one Chemical compound C\C=C\C(=O)C1=C(C)CCCC1(C)C BGTBFNDXYDYBEY-FNORWQNLSA-N 0.000 description 2
- ORMHZBNNECIKOH-UHFFFAOYSA-N 4-(4-hydroxy-4-methylpentyl)cyclohex-3-ene-1-carbaldehyde Chemical compound CC(C)(O)CCCC1=CCC(C=O)CC1 ORMHZBNNECIKOH-UHFFFAOYSA-N 0.000 description 2
- KZZASWGRLOTITL-UHFFFAOYSA-N 4-cyclohexyl-2-methylbutan-2-ol Chemical class CC(C)(O)CCC1CCCCC1 KZZASWGRLOTITL-UHFFFAOYSA-N 0.000 description 2
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical compound O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 2
- 241000468081 Citrus bergamia Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- 241000721662 Juniperus Species 0.000 description 2
- 235000017858 Laurus nobilis Nutrition 0.000 description 2
- 244000147568 Laurus nobilis Species 0.000 description 2
- 244000246386 Mentha pulegium Species 0.000 description 2
- 235000016257 Mentha pulegium Nutrition 0.000 description 2
- 235000004357 Mentha x piperita Nutrition 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OEYQBKYISMRWQB-UHFFFAOYSA-N Santal Chemical compound C=1C(OC)=CC(O)=C(C2=O)C=1OC=C2C1=CC=C(O)C(O)=C1 OEYQBKYISMRWQB-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 244000172533 Viola sororia Species 0.000 description 2
- 235000006886 Zingiber officinale Nutrition 0.000 description 2
- 244000273928 Zingiber officinale Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 2
- 229940116229 borneol Drugs 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 229940043350 citral Drugs 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003818 flash chromatography Methods 0.000 description 2
- 238000007701 flash-distillation Methods 0.000 description 2
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 2
- 235000008397 ginger Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 235000001050 hortel pimenta Nutrition 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- UWKAYLJWKGQEPM-UHFFFAOYSA-N linalool acetate Natural products CC(C)=CCCC(C)(C=C)OC(C)=O UWKAYLJWKGQEPM-UHFFFAOYSA-N 0.000 description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- CZCBTSFUTPZVKJ-UHFFFAOYSA-N rose oxide Chemical compound CC1CCOC(C=C(C)C)C1 CZCBTSFUTPZVKJ-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 150000003509 tertiary alcohols Chemical class 0.000 description 2
- NPNUFJAVOOONJE-ZIAGYGMSSA-N β-(E)-Caryophyllene Chemical compound C1CC(C)=CCCC(=C)[C@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-ZIAGYGMSSA-N 0.000 description 2
- OOEDQCLPDCXMMC-UHFFFAOYSA-N (3,5,10,10-tetramethylspiro[5.5]undec-2-en-11-yl) acetate Chemical compound CC1CC(C)=CCC11C(OC(C)=O)C(C)(C)CCC1 OOEDQCLPDCXMMC-UHFFFAOYSA-N 0.000 description 1
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 1
- HUWSZNZAROKDRZ-RRLWZMAJSA-N (3r,4r)-3-azaniumyl-5-[[(2s,3r)-1-[(2s)-2,3-dicarboxypyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]amino]-5-oxo-4-sulfanylpentane-1-sulfonate Chemical compound OS(=O)(=O)CC[C@@H](N)[C@@H](S)C(=O)N[C@@H]([C@H](C)CC)C(=O)N1CCC(C(O)=O)[C@H]1C(O)=O HUWSZNZAROKDRZ-RRLWZMAJSA-N 0.000 description 1
- KHWTYGFHPHRQMP-UHFFFAOYSA-N (4-propan-2-ylcyclohexyl)methanol Chemical compound CC(C)C1CCC(CO)CC1 KHWTYGFHPHRQMP-UHFFFAOYSA-N 0.000 description 1
- WEFHSZAZNMEWKJ-KEDVMYETSA-N (6Z,8E)-undeca-6,8,10-trien-2-one (6E,8E)-undeca-6,8,10-trien-2-one (6Z,8E)-undeca-6,8,10-trien-3-one (6E,8E)-undeca-6,8,10-trien-3-one (6Z,8E)-undeca-6,8,10-trien-4-one (6E,8E)-undeca-6,8,10-trien-4-one Chemical compound CCCC(=O)C\C=C\C=C\C=C.CCCC(=O)C\C=C/C=C/C=C.CCC(=O)CC\C=C\C=C\C=C.CCC(=O)CC\C=C/C=C/C=C.CC(=O)CCC\C=C\C=C\C=C.CC(=O)CCC\C=C/C=C/C=C WEFHSZAZNMEWKJ-KEDVMYETSA-N 0.000 description 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- JHEPBQHNVNUAFL-AATRIKPKSA-N (e)-hex-1-en-1-ol Chemical compound CCCC\C=C\O JHEPBQHNVNUAFL-AATRIKPKSA-N 0.000 description 1
- KHLFMZDGADSQGR-UHFFFAOYSA-N 1-oxacyclohexadec-3-en-2-one Chemical compound O=C1OCCCCCCCCCCCCC=C1 KHLFMZDGADSQGR-UHFFFAOYSA-N 0.000 description 1
- UEGBWDUVDAKUGA-UHFFFAOYSA-N 2,6,10-trimethylundec-9-enal Chemical compound CC(C)=CCCC(C)CCCC(C)C=O UEGBWDUVDAKUGA-UHFFFAOYSA-N 0.000 description 1
- USMNOWBWPHYOEA-UHFFFAOYSA-N 3‐isothujone Chemical compound CC1C(=O)CC2(C(C)C)C1C2 USMNOWBWPHYOEA-UHFFFAOYSA-N 0.000 description 1
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 1
- ZXCVFSSIAOEEFK-UHFFFAOYSA-N 5,10,10-trimethylspiro[5.5]undec-2-en-11-ol Chemical compound CC1CC=CCC11C(O)C(C)(C)CCC1 ZXCVFSSIAOEEFK-UHFFFAOYSA-N 0.000 description 1
- AZUVBPVDRHGGEP-UHFFFAOYSA-N 6a,9a-dimethyl-4,5,7,8,9,9a-hexahydro-6aH-dipyrrolo(2,3-b;3',2',1'-hi)indole Natural products CC(=C)C1CCC(C)=CCCC(C)=CCCC(C)=CC1O AZUVBPVDRHGGEP-UHFFFAOYSA-N 0.000 description 1
- MUPVFPUVXNUKTH-UHFFFAOYSA-N 7,9,10-trimethylspiro[4.5]dec-7-en-4-one Chemical compound CC1C(C)C=C(C)CC11C(=O)CCC1 MUPVFPUVXNUKTH-UHFFFAOYSA-N 0.000 description 1
- NVEQFIOZRFFVFW-UHFFFAOYSA-N 9-epi-beta-caryophyllene oxide Natural products C=C1CCC2OC2(C)CCC2C(C)(C)CC21 NVEQFIOZRFFVFW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- YPZUZOLGGMJZJO-UHFFFAOYSA-N Ambronide Chemical compound C1CC2C(C)(C)CCCC2(C)C2C1(C)OCC2 YPZUZOLGGMJZJO-UHFFFAOYSA-N 0.000 description 1
- 235000009051 Ambrosia paniculata var. peruviana Nutrition 0.000 description 1
- 206010002653 Anosmia Diseases 0.000 description 1
- 235000003097 Artemisia absinthium Nutrition 0.000 description 1
- 240000001851 Artemisia dracunculus Species 0.000 description 1
- 235000017731 Artemisia dracunculus ssp. dracunculus Nutrition 0.000 description 1
- 235000003261 Artemisia vulgaris Nutrition 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- 240000007436 Cananga odorata Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000544656 Cedrus atlantica Species 0.000 description 1
- 235000013306 Cistus creticus Nutrition 0.000 description 1
- 244000028508 Cistus creticus Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 241000675108 Citrus tangerina Species 0.000 description 1
- 235000006965 Commiphora myrrha Nutrition 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 240000002943 Elettaria cardamomum Species 0.000 description 1
- 241000116713 Ferula gummosa Species 0.000 description 1
- 241000628997 Flos Species 0.000 description 1
- 240000006927 Foeniculum vulgare Species 0.000 description 1
- 235000004204 Foeniculum vulgare Nutrition 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- WSTYNZDAOAEEKG-UHFFFAOYSA-N Mayol Natural products CC1=C(O)C(=O)C=C2C(CCC3(C4CC(C(CC4(CCC33C)C)=O)C)C)(C)C3=CC=C21 WSTYNZDAOAEEKG-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 240000009023 Myrrhis odorata Species 0.000 description 1
- 235000007265 Myrrhis odorata Nutrition 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241001104043 Syringa Species 0.000 description 1
- 241000775848 Syringa oblata Species 0.000 description 1
- 235000004338 Syringa vulgaris Nutrition 0.000 description 1
- 240000000785 Tagetes erecta Species 0.000 description 1
- 235000012311 Tagetes erecta Nutrition 0.000 description 1
- 235000003595 Tagetes minuta Nutrition 0.000 description 1
- 235000008109 Thuja occidentalis Nutrition 0.000 description 1
- 240000003243 Thuja occidentalis Species 0.000 description 1
- 235000007303 Thymus vulgaris Nutrition 0.000 description 1
- 240000002657 Thymus vulgaris Species 0.000 description 1
- 241000414043 Vetiveria Species 0.000 description 1
- 241000947655 Wardia Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- FAMPSKZZVDUYOS-UHFFFAOYSA-N alpha-Caryophyllene Natural products CC1=CCC(C)(C)C=CCC(C)=CCC1 FAMPSKZZVDUYOS-UHFFFAOYSA-N 0.000 description 1
- GUUHFMWKWLOQMM-NTCAYCPXSA-N alpha-hexylcinnamaldehyde Chemical compound CCCCCC\C(C=O)=C/C1=CC=CC=C1 GUUHFMWKWLOQMM-NTCAYCPXSA-N 0.000 description 1
- GUUHFMWKWLOQMM-UHFFFAOYSA-N alpha-n-hexylcinnamic aldehyde Natural products CCCCCCC(C=O)=CC1=CC=CC=C1 GUUHFMWKWLOQMM-UHFFFAOYSA-N 0.000 description 1
- 235000019558 anosmia Nutrition 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000001138 artemisia absinthium Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000001053 badasse Nutrition 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 1
- NPNUFJAVOOONJE-UHFFFAOYSA-N beta-cariophyllene Natural products C1CC(C)=CCCC(=C)C2CC(C)(C)C21 NPNUFJAVOOONJE-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 235000005300 cardamomo Nutrition 0.000 description 1
- NPNUFJAVOOONJE-UONOGXRCSA-N caryophyllene Natural products C1CC(C)=CCCC(=C)[C@@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-UONOGXRCSA-N 0.000 description 1
- 229940117948 caryophyllene Drugs 0.000 description 1
- 210000000085 cashmere Anatomy 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- XTUCGACHIRHVPO-UOHALXPSSA-N cedroxide Chemical compound C([C@@]1(C)OC2)C[C@@]34[C@H](C)CCC4[C@H]2[C@H]1C3 XTUCGACHIRHVPO-UOHALXPSSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- UZFFFFWQKMPLAC-UHFFFAOYSA-N dec-7-enal Chemical compound CCC=CCCCCCC=O UZFFFFWQKMPLAC-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000004864 galbanum Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- HIGQPQRQIQDZMP-UHFFFAOYSA-N geranil acetate Natural products CC(C)=CCCC(C)=CCOC(C)=O HIGQPQRQIQDZMP-UHFFFAOYSA-N 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- HIGQPQRQIQDZMP-DHZHZOJOSA-N geranyl acetate Chemical compound CC(C)=CCC\C(C)=C\COC(C)=O HIGQPQRQIQDZMP-DHZHZOJOSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002561 ketenes Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 244000056931 lavandin Species 0.000 description 1
- 235000009606 lavandin Nutrition 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 229930007744 linalool Natural products 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000008368 mint flavor Substances 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229930007790 rose oxide Natural products 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- UPCZZRYVGMWWQV-UHFFFAOYSA-N spiro[4.5]dec-8-en-4-one Chemical class O=C1CCCC11CC=CCC1 UPCZZRYVGMWWQV-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930007110 thujone Natural products 0.000 description 1
- 239000001585 thymus vulgaris Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
- C07C35/23—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/18—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/18—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C43/188—Unsaturated ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/385—Saturated compounds containing a keto group being part of a ring
- C07C49/417—Saturated compounds containing a keto group being part of a ring polycyclic
- C07C49/423—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system
- C07C49/427—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having two rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/385—Saturated compounds containing a keto group being part of a ring
- C07C49/417—Saturated compounds containing a keto group being part of a ring polycyclic
- C07C49/423—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system
- C07C49/427—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having two rings
- C07C49/447—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having two rings the condensed ring system containing ten carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/613—Unsaturated compounds containing a keto groups being part of a ring polycyclic
- C07C49/617—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system
- C07C49/623—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system having two rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/613—Unsaturated compounds containing a keto groups being part of a ring polycyclic
- C07C49/617—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system
- C07C49/623—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system having two rings
- C07C49/637—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system having two rings the condensed ring system containing ten carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/013—Esters of alcohols having the esterified hydroxy group bound to a carbon atom of a ring other than a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings
- C11B9/0046—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings
- C11B9/0057—Spiro compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/50—Spiro compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Fats And Perfumes (AREA)
- Cosmetics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Detergent Compositions (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The present invention relates to the perfumery industry. It concerns more particularly an alcohol, ester, ether or ketone derivative having a spiro-type skeleton, the latter being substituted by short alkyl groups. The invention also relates to the use of the invention compounds as perfuming ingredients, able to impart a woody and/or aromatic, as well as to the perfumed articles or perfuming compositions comprising as active ingredient a compound of formula (I).
Description
Technical field
The present invention relates to perfume industry.More specifically to alcohol, ester, ether or ketone derivatives with a volution type skeleton, and it is as fragrant composition (perfuming ingredient).The invention still further relates to and comprise as the perfuming article (perfumed articles) of the The compounds of this invention of activeconstituents or send out composition fragrant.
Background technology
Alcohol, ester, ether or ketone derivatives with a volution type skeleton is the known chemical class in this area.Yet, and surprisingly, although reported a large amount of structures in the technology formerly, it is known that the compound of several formulas that describe below (I) structure is only arranged.
For example, Novikova etc. are in their Naftekhimiya, 1984, open in 24,475 articles, as 2 of chemical intermediate, 8-dimethyl spiral shell [5,5] 11 carbon-8-alkene-1-ketone and 2,9-dimethyl spiral shell [5,5] the ketone mixture of 11 carbon-8-alkene-1-ketone, and 1,9-dimethyl spiral shell [5,5] 11 carbon-8-alkene-1-pure and mild 1, the tertiary alcohol mixture of 8-dimethyl spiral shell [5,5] 11 carbon-8-alkene-1-alcohol.Same author is at Naftekhimiya, and 1986,
26, open in 3 articles, remain as 1 of chemical intermediate, 7-dimethyl spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-is pure and mild 1, the tertiary alcohol mixture of 8-dimethyl spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-alcohol.
In addition, Nakamura etc. are at Chem.Commun, and are open in 2002,1648, as 2 spiral shell ketones of chemical compound, and 8,9-dimethyl spiral shell [5,5] 11 carbon-8-alkene-1-ketone and 7,8-dimethyl spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-ketone.
Yet, in any above-mentioned article, all do not mention or hint specific organoleptic characteristic of The compounds of this invention, or mention or hint the potential purposes of described compound as fragrant composition.
In compound, seldom know the taste that it might be useful to perfume industry in the prior art with the structure that is similar to The compounds of this invention.At US 4,668,432 have reported oxygen base spiral shell [4,5] that some alkyl replaces last of the ten Heavenly stems-7-alkene (oxo-spiro[4,5] dec-7-ene) derivative, and it has by preceding flavor mint flavor or animal (top-note) and to account for leading taste.Similarly, US 4,622, and 172 disclose 9-methyl isophthalic acid 1-sec.-propyl-spiral shell [5,5] 11 carbon-8-alkene, and it gives fresh peppermint of composition one and pungent fragrance.At US 4,668,432 and US 4,622,172 in disclosed compound all have structure different and taste with The compounds of this invention.
Summary of the invention
We have determined the compound of following formula now surprisingly:
Wherein m represents 0 or 1;
R represents hydrogen atom or methyl or ethanoyl;
R
1, R
2And R
4Represent hydrogen atom or methyl;
R
3Represent hydrogen atom, or methyl or ethyl; Whole R
1, R
2, R
3And R
4In 2,3 or 4 represent a group that comprises at least one carbon atom simultaneously; And be under 0 the situation at n, wavy line and the two keys of dotted line representative; Or
Be that wavy line is represented singly-bound under 1 the situation at n; And dotted line is represented singly-bound or two key;
The useful aromatic property that has xyloid and/or fragrant type makes them very useful on perfume industry.
It will be appreciated that, in formula (I) compound, described each R
1Or R
3Can be respectively and other R
1Or R
3Identical or different.And formula (I) compound can be with its optical isomer or its diastereomer or even arbitrary form of arbitrary mixture of described isomer.
And, by the composition that at least 2 formulas (I) compound is formed, also refer to the mixture of formula (I) compound from now on, and the mixture of regional isomer preferably, also be useful fragrant composition and be a part of the present invention therefore." regional isomer " means such compound here, and they are according to one of them or more R
3(R
3Do not represent hydrogen atom) different with volution skeleton bonded position.As the unrestriced example of " regional isomer ", can enumerate 6,8,10-trimethylammonium-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-ketone (6,8,10-trimethyl-spiro[4,5] 10-trimethylammonium-spiral shell [4 dec-7-en-1-one) and its regional isomer 7,9,, 5] last of the ten Heavenly stems-7-alkene-1-ketone (7,9,10-trimethyl-spiro[4,5] dec-7-en-1-one).
The mixture of preferred formula (I) compound is that those comprise in essence, for example as main component, and 2 regional isomers of formula (I).
By following formula: compound another embodiment of the invention is described:
Wherein, n, m, R, R
1, R
3, wavy line and dotted line have with formula (I) in the identical implication that shows.
Preferably, formula (II) compound is those m and n and dotted line and the middle identical compound of implication of wavy line and formula (I);
R represents hydrogen atom or ethanoyl;
R
1And R
3Represent hydrogen atom or methyl; Whole R
1And R
32,3 or 4 represent methylidenes simultaneously, and whole R
31,2 or 3 (preferably non-conterminous) represent methylidene simultaneously.
Another preferred embodiment of The compounds of this invention is formula (II) compound, wherein m, n and dotted line and wavy line have with formula (I) in identical implication; And
R represents hydrogen atom or ethanoyl;
A R
1Be hydrogen atom and another R
1Represent hydrogen atom or methyl;
R
3Represent hydrogen atom or methyl or ethyl; Whole R
1And R
32,3 or 4 for comprising a group of at least one carbon atom, and whole R
31,2 or 3 (preferably non-conterminous) represent methylidene or ethyls.
Should be understood that, for formula (II) compound, described each R
1Or R
3Can be respectively and other R
1Or R
3Identical or different.
The alcohol of through type (III) or ester illustrate very valuable embodiment of the present invention:
Wherein R represents hydrogen atom or ethanoyl; And
R
3For identical and represent hydrogen atom or R
3For difference and represent hydrogen atom or methyl.
Perhaps, the ketone by formula (IV) illustrates another useful embodiment of the present invention
2 best non-conterminous R wherein
3Represent methylidene and other R
3Represent hydrogen atom.
Perhaps, also can quote the formula V compound
Wherein R represents hydrogen atom or ethanoyl;
R
1Represent hydrogen atom or methyl; And
R
3Represent hydrogen atom or methyl or ethyl and at least 2 R
3Represent methylidene; And
M be 1 and dotted line represent singly-bound, or
M is 0 and the two keys of dotted line representative.
Formula (II), (III), (IV) and (V) compound just as formula (I) compound, can be the arbitrary forms with its optical isomer or its diastereomer or its mixture.
Spirocyclic compound of the present invention can be by relating at the ketenes (enone) of formula (VI) or as selection, and the thermocatalysis between the diene of Mannich base of its formula of equal value (VII) (Mannich base) and formula (VIII) or the Diels-Alder reaction of Louis acid catalysis obtain:
Wherein m and R
1, R
2And R
3Be suc as formula (I) definition, and if say R independently
5If represent methylidene, ethyl, propyl group or sec.-propyl are or to amount to R with their bonded nitrogen-atoms
5Represent C
5-C
7Saturated heterocycle, for example morpholine, piperidines or tetramethyleneimine;
And the diene of formula (VIII)
R wherein
2Suc as formula (I) definition,
So that a spirocyclic ketone (IX) to be provided
Wherein m and R
1, R
2And R
3Define suc as formula (I).
The typical catalyzer that can be used for acid catalyzed Di Ersi-Alder (reaction) is AlCl
3, FeCl
3Or BF
3Et
2O.
The temperature of reaction of Di Ersi-Alder depends on the type of catalyzer.Under the situation of thermal response, temperature range is between 100 ℃~240 ℃, is preferably between 140 ℃~200 ℃.Using under the lewis acidic situation, temperature range is-40 ℃~30 ℃, is preferably-30 ℃~20 ℃.
Diels-Alder reaction can be carried out not having solvent or exist under the solvent.When using solvent, as long as solvent is fit to initiator and product, any existing solvent in Diels-Alder reaction all can be used for purpose of the present invention so.Unrestriced embodiment comprises aromatic solvent, for example toluene or dimethylbenzene, or selectively, be used for acid catalyzed reaction, can use for example CH
2Cl
2, toluene or CH
3The solvent of CN.
Should be understood that also that when diene (VIII) when being not symmetrical compound Diels-Alder reaction may cause the formation of mixture of the volution ketone of formula (IX), the more precisely mixture of regional isomer.In addition because spirocyclic ketone (IX) has several chiral centres, therefore described ketone can with the mixture of optically active isomer or diastereomer or even the form of arbitrary mixture of described isomer obtain.
As is known to the person skilled in the art, the comparing of all possible isomer of acquisition may be depended on initial compounds (VIII) and (VI) or character (VII), and depends on experiment condition, also may depend on the character of the catalyzer of use.
Therefore, for example use basic metal, for example LiAlH
4Hydride or the alkylating reagent of MeLi for example, the spirocyclic ketone of acquisition (IX) can be reduced into corresponding formula (X) volution alcohol subsequently.
Wherein m and R
1, R
2, R
3And R
4Identical meanings with expression in the formula (I).
If desired, using and well known to a person skilled in the art traditional method, can be ester or ether with volution alcohol (X) subsequent transformation.If desired, also can be by the carbon-carbon double bond reduction of hydrogenization with spirocyclic ketone (IX) or volution alcohol (X) or derivatives thereof.
Schema (1) has provided a specific embodiment of entire method:
Schema (1): the embodiment of the synthetic route of formula (I) compound
As discussed previously, formula (I) compound has makes its odor property very useful on perfume industry.More precisely, formula (I) compound presents xyloid and/or fragrant fragrance, and does not have the peppermint or the typical taste profile of animal of Spirocyclic derivatives in the above-mentioned prior art.New compound with this odor property is that perfume industry is in demand.
The embodiment of The compounds of this invention is various, will be more clear among description below and the embodiment.
An embodiment is 2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester (2,2,9,11-tetramethylspiro[5,5] undec-8-en-1-yl acetate).Described compound has very dense woody odor, and outstanding amber/grane ambra intension (connotation) is arranged.This amber/grane ambra taste, it is very strong and strong, all is very easy consciousness as preceding flavor (top note) and aftertaste (bottom note).Whole taste make us remembering Amberwood (source: BASF AG) or 8,13:13,20-bis-epoxy-15,16-dinorlabdane (source: taste Firmenich SA).Except its outstanding taste, unlike the compound of same sense of smell family (olfactive family) in many prior aries, 2,2,9, as if 11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester also have the advantage of not inducing anosmia.
Compound of the present invention and another embodiment that belongs to wooden sense of smell family together are 2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-alcohol (2,2,11-trimethylspiro[5,5] undec-8-en-1-ol), it has outstanding wooden taste, and camphor and earth smell are arranged.The feature of whole taste is making very much of a kind of patchoulicvetyver type interior perfume (or spice) (undernote) smell that the people appreciates and real Moschus and wooden-root, makes us remembering Tonalide
(source: PFW Holland), smells at one and to be with whole smell more than the sustainable week.Because fragrant in it is distinctive, 2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-alcohol has outstanding ability and gives strong, dense (volume) and the persistence of sending out composition fragrant.
The saturated analogues of aforesaid compound, promptly 2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-1-alcohol (2,2,11-trimethylspiro[5,5] undec-1-ol), have and be very similar to 2,2, the taste of 11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-alcohol, but it is drier.
2,2,7,9-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone and its regional isomer 2,2,8, the mixture of 10-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone have very complicated taste type, but belong to aromatic series clearly.That the fragrance of described mixture has is fragrance, pungent, cardamom and terpenic smell, and the intension of fragrant and sulphur makes whole smell make us remembering eucalyptus and Salvia japonica Thunb. volatile oil in and the camphor-xyloid.Described mixture is extremely appreciated by the perfumer owing to its very useful aromatic odour, and it makes the people remember the taste of valuable Laurus nobilis volatile oil, and Laurus nobilis volatile oil only can use with very limited amount.And, found that the characteristic of described mixture in the function spices of for example softening agent or sanitising agent is significant when comparing with the product of other same sense of smell families.
The low analogue of said mixture for example only has 3 or 2 methyl substituted analogues, has the taste of trend distinct fragrance smell, and more tends to camphoraceous and evaporable taste more than previous compound.For example, 2,2,10-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-ketone and 2,2,7-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-ketone has pleasant and natural fragrance, it has than above-mentioned its tetramethyl-analogue more manys camphor, wooden, juniper and lavender taste, and 2,2-dimethyl spiral shell [5,5] 11 carbon-8-1-ketone has the smell of polyterpene (terpeny) more, camphor, earth and slight Flower of Aztec Marigold than above-mentioned its tetramethyl-analogue.
Another example of the mixture of formula (I) compound is a regional isomer 6,8-dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-base acetic ester and 7,9-dimethyl-spiral shell [4,5] last of the ten Heavenly stems-mixture of 7-alkene-1-base acetic ester, it has, and intensive is wooden, China fir and amber taste, with the sawdust intension.
As example, can quote (1RS, 6RS with formula (I) compound of specific diastereomeric form, 11RS)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester and (1RS, 6SR, 11SR)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester, they have good wooden and amber taste, back one compound since its denseer taste and more the perfumer like.In addition, also can quote (1RS, 6RS, 11RS)-2,2, and 11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-alcohol, it is above-mentioned 2,2 that it has how wooden taste and slight ratio, 11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-alcohol Wrinkled Gianthyssop Herb flavor still less.
Therefore, of the present invention one significant especially embodiment for the perfumer, is 2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester or 2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-alcohol or 2,2,7,9-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone and 2,2,8, the mixture of 10-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone.Similarly, a significant embodiment of the present invention is 2,2,11-trimethylammonium spiral shell [5,5] undecane-1-alcohol, 2,2-dimethyl spiral shell [5,5] 11 carbon-8-alkene-1-ketone, (1RS, 6SR, 11SR)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester, (1RS, 6RS, 11RS)-2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-alcohol, (1RS, 6RS, 11RS)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester, or 2,2,10-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-ketone and 2,2,7-trimethylammonium spiral shell [5,5] mixture of 11 carbon-8-alkene-1-ketone, or 6,8-dimethyl-spiral shell [5,5] last of the ten Heavenly stems-7-alkene-1-base acetic ester and 7, the mixture of 9-dimethyl-spiral shell [5,5] last of the ten Heavenly stems-basic acetic ester of 7-alkene-1-.Another relevant embodiment of the present invention is a compound 2,6, and 8-trimethylammonium-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-alcohol or 7-ethyl-11-methyl-spiral shell [5,5] 11 carbon-1-alcohol will be further described below.
As mentioned above, the invention still further relates to the purposes of the mixture of formula (I) compound or formula (I) compound as fragrant composition.In other words, it relates to and gives, strengthens, improves or modify the method for sending out composition fragrant or sending out the characteristic of perfumery product, and this method is included in the compound of the same form at least (I) of adding significant quantity in described composition or the article.Should be understood that here that for " use of the same form (I) compound at least " use one or more formulas (I) compound with its any form, it can be used as activeconstituents and uses easily in spices.
Described form also is a purpose of the present invention.
In one embodiment of the invention, the described form of can be easily using as fragrant composition a kind of is to comprise the composition of the material of the same form (I) compound and at least one fragrance carrier at least.For " fragrance carrier ", mean one or more here can not change the material that it influences the organoleptic property significantly with at least one compound of the present invention, for example, is actually the neutral material from the viewpoint of spices.Described carrier can be a liquid or solid.
As liquid vehicle, can quote emulsification system, i.e. solvent and surfactant system, or the solvent that in spices, uses usually as unrestricted embodiment.Example as the solvent that generally is used for spices, in general, can quote for example dipropylene glycol, diethyl phthalate, Isopropyl myristate, phenylformic acid Bian ester, 2-(2-ethoxy ethoxy)-1-ethanol or ETHYL CTTRATE, these all are the most frequently used.As solid carrier, can quote a kind of absorption resin or polymkeric substance as unrestricted embodiment, or packaged material, described material is well known to a person skilled in the art.
In another embodiment of the invention, the form that the another kind of The compounds of this invention is fit to is to comprise the material of the same form (I) compound and the composition of spices matrix at least, or the composition of above-mentioned substance and spices matrix.In other words, compound (I) is the form with the flavor compositions that contains at least one compound of the present invention as fragrant composition.Should be understood that this fragrant composition exists to send out significant quantity fragrant.
Generally speaking, mean here and contain accompany composition (perfuming co-ingredient) and may one or more normally used solvent or assistant agents in perfume industry of at least one perfume (or spice) for " spices matrix ".
Described perfume (or spice) composition of accompanying is not formula (I) compound.And, mean a compound that in perfume industry, uses at present here for " send out perfume (or spice) accompany composition ", promptly in sending out fragrant preparation or in for the composition that gives the enjoyment effect as the compound of composition use.In other words, this composition of accompanying is considered to send out a fragrant composition, and must be thought by those skilled in the art can be with positive or pleasant mode gives or the taste of modifying composition, and not merely be flavoursome.Here it is to be further understood that, unless show in addition or describe, any mixture that from chemosynthesis, directly obtains (for example not having purifying), compound of the present invention will be referred to as initial intermediate or as the finished product in described chemosynthesis, and these mixtures can not be considered to send out composition fragrant according to of the present invention.
Characteristic and the type of the sending out the fragrant composition of accompanying that are present in the matrix here no longer are described in more detail, in any case they all can not limit, those skilled in the art can be on its common Knowledge Base and be selected according to planning the sensory effects of use or application and needs.Under usual conditions, these perfume (or spice) are accompanied and are become to belong to various alcohol, aldehyde, ketone, ester, ether, acetic ester, nitrile, terpene hydrocarbon, heterogeneous ring compound nitrogenous or the sulfur-bearing xanthin and the chemical species of volatile oil, and described perfume (or spice) composition of accompanying can be natural or synthetic source.Many these composition of accompanying is enumerated in book of reference, for example by the outstanding Perfume and Flavor Chemicals of S.Arctander, 1969, Montclair, New Jersey, in the book of USA or in its nearer version, or in other similar works, and in a large amount of patent documentation of field of perfumery.It is to be further understood that the described composition of accompanying also can be the known compound that discharges various types of aroma compounds with control mode.
Similarly, the detailed description of the characteristic of normally used solvent and type can not limit in sending out perfume base matter, and those skilled in the art can select on the basis of the characteristic of the product of wanting perfuming.Yet,, except that above mentioned solvent, can also quote ethanol, water/ethanol mixture, Limonene or other terpenes, those known Isopar for example as the unrestricted embodiment of normally used solvent in spices matrix
Board (source: isoparaffin Exxon Chemical), or those known Dowanol for example
Board (source: Dow Chemical Company) glycol ether and glycol ether ester.
It is of the present invention that to send out composition fragrant can be the simple mixture of various accompany composition and solvents, or with the two-phase system of for example emulsion or microemulsion.Perhaps, describedly send out composition fragrant and can merge to as mentioned above in the solid spice carrier.
Here it should be noted in the composition of above-mentioned substance, the possibility that has more than a kind of formula (I) compound is important, because it makes the perfumer can prepare mediation spices (accords), essence, it has the taste tone of various The compounds of this invention, has therefore created new instrument for their work.
And as mentioned above, formula (I) compound is a useful fragrant composition, and all areas that therefore can be advantageously used in modern spices adds formula (I) compound with any its form therein positively to give or to modify the taste of the consumer's goods.Therefore, comprise
1) same form (I) compound at least, or the composition of above-mentioned substance; And
2) consumer's goods matrix,
The perfuming article also be one object of the present invention.
For clearer, must should be mentioned that also mean consuming product here for " consumer's goods matrix ", i.e. the consumable product of sanitising agent or perfume for example.In other words, with any its form according to perfuming article of the present invention, consist essentially of the function prescription, and useful reagent that can be randomly other, the corresponding for example consuming product of the needs of sanitising agent, and at least one The compounds of this invention of sense of smell significant quantity.
Characteristic and type that consuming product constitute here no longer are described, in any case be to be difficult to limit, those skilled in the art can be on the basis of its common knowledge and the characteristic and the effect of described product as required select.
The example of the consuming product of suitable not perfuming comprises solid and liquid cleaner and textile softener, and other article common in field of perfumery, i.e. treatment, skin care product, reodorant or antiperspirant, air freshener and the cosmetic formulations of perfume, Gulong perfume and the liquid that shaves, perfumed soap, body wash or bath salt, mousse, oil or gel, health product or for example shampoo.As sanitising agent, no matter they are domestic use or industrial use, and for example cleanser compositions that use or the cleaning product that is used to clean or be used to clean the cleaning product on various surfaces for example are intended for use textiles, plate or hard surface and handle.Other perfuming article are textiles freshener, Ironing water, paper, rag or SYNTHETIC OPTICAL WHITNER.
Some above-mentioned consumer's goods matrix can provide corrosive medium for The compounds of this invention, and Bao Zhuan example for example is so that be not essential by premature decomposition for the protection The compounds of this invention.
The ratio that compound of the present invention is attached in above-mentioned various article or the composition changes in a wide numerical range.Range of concentrations depends on the character of the The compounds of this invention of use, the character of product of wanting perfuming and the aroma effect of needs, when The compounds of this invention with prior art in normally used perfume (or spice) accompany the form of mixture of composition, solvent and additive when using, its concentration range also depends on the character of the composition of accompanying in the composition that provides.
For example, these compounds can typically use in the concentration range of 0.01%~10.0% (weight).Preferably, for the The compounds of this invention of overpowering odor or the mixture of compound, The compounds of this invention typical concn scope is 0.1%~3% (weight meter), and for lighter smell, preferably uses in the concentration range of 0.5%~5% (weight).All above-mentioned percentage ratios all are to represent with the weight of sending out composition fragrant that wherein is added with The compounds of this invention.
When these compounds are directly used in sending out of above-mentioned some consumer's goods when fragrant, can use with the concentration lower than above-mentioned concentration.
To describe the present invention in detail by following embodiment now, abbreviation wherein has the common implication in this area, temperature with degree centigrade (℃) expression; The NMR spectroscopic data uses the 360MHz machine at CDCl
3In record, chemistry replaces δ and represents that with the ppm as the TMS of standard coupling constant J represents with Hz and all abbreviations have the common implication in this area.
Embodiment
Embodiment 1
Some compounds of the present invention or synthesizing as the useful compound of intermediate
A) 7,9-dimethyl-spiral shell [5,5] 11 carbon-8-alkene-ketone and 8, the mixture of 10-dimethyl-spiral shell [5,5] last of the ten Heavenly stems-8-alkene-ketone
With pimelinketone (1529g; 15.6mol), the 2-methyl isophthalic acid, 3-pentadiene (984g; 12mol), BHT (2.4g) and 37% formalin (488g; 180.56g pure formaldehyde; 6.02mol) in the 5 liters of stainless steel pressure kettle of packing into, mixture is heated to 200 ℃ kept 7 hours under stirring action.After being cooled to room temperature, aqueous phase discarded is washed organic phase with salt, obtains crude product.Crude product is distilled (B.p.=82 ℃ by the 70cmSulzer post; 1mbar) obtain the pure product of 447.5g, pure product are that 4 ratios are 4/7/55/34 mixture of isomers, and yield is 38.7%.
Organoleptics property: with plant and the woody odor draft intension.
MS (main isomer): 39 (15); 41 (24); 55 (17); 67 (49); 77 (20); 79 (20); 82 (100); 91 (28); 93 (23); 105 (13); 107 (18); 111 (10); 119 (6); 121 (11); 135 (9); 149 (16); 159 (5); 163 (8); 174 (2); 177 (8); 192 (M+, 19).
MS (the second main isomer): 39 (30); 41 (44); 55 (30); 67 (64); 77 (37); 79 (37); 82 (100); 91 (53); 93 (41); 105 (28); 107 (44); 109 (12); 119 (19); 121 (24); 135 (42); 149 (32); 150 (6); 159 (15); 163 (19); 174 (6); 177 (20); 192 (M+, 34).
(1H-NMR:5.27 isomer C) and 5.18 (isomer D) (br s, 1H); 2.60-1.43 (m, 11H); 1.64 (s, 3H); 1.37-1.20 (m, 2H); (0.83 isomer D) (d, J=7Hz, 3H); (0.78 isomer C) (d, J=7Hz, 3H).
B) (5RS, 6SR, 10SR)-10-ethyl-6,8-dimethyl spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-ketone
With propylidene cyclopentanone (E/Z:9/1) (248g; 2mol) pack in many mouthfuls of 2 liters of round-bottomed flasks and solution is cooled to 0 ℃ with toluene (200ml).Dropwise add BF with the time more than 25 minutes
3Etherate (20ml) keeps reaction mixture at 0 ℃ simultaneously.Continue to stir 1 hour at 0 ℃, dropwise be added in 2-methyl isophthalic acid in the toluene (200ml), 3-pentadiene (410g with the time more than 3 hours subsequently; 5mol) solution.Then reaction mixture is poured on ice after 3 hours 0 ℃ of stirring.Aqueous phase discarded, water, Na
2CO
3The aqueous solution and salt washing organic phase.Use MgSO
4Drying also removes by filter the thick cycloaddition compound of solvent acquisition.By the cycloaddition compound of flash distillation acquisition with mixture of isomers (79/5/16) form, yield is 81.4% with the 10cmVigreux post, then carries out the distillation second time.By 35cmFischer Spaltrohr
The back single flash of post can be isolated main isomer, is the compound of title.
Organoleptics property: with the Salvia japonica Thunb. smell of fruity and damascone (damascone) intension.
MS:27(51);29(51);39(54);41(80);43(31);51(14);53(29);55(44);65(35);67(77);69(11);77(47);79(43);82(100);91(68);93(40);96(55);105(38);107(55);111(14);119(17);121(35);125(34);133(19);135(34);149(38);159(52);163(33);173(12);177(74);188(25);191(11);206(16)。
1H-NMR:5.27(br?s,1H);2.38-2.27(m,1H);2.20-2.00(m,3H);1.92-1.70(m,5H);1.65(s,3H);1.46(dd,J=17Hz,12Hz,1H);1.32-1.21(m,1H);1.06-0.75(m,1H);0.91(t,J=8Hz,3H);0.87(d,J=8Hz,3H)。
13C-NMR:222.7(s);132.2(s);124.9(d);55.1(s);39.6(t);35.9(d);34.2(d);33.4(t);29.9(t);23.9(t);23.3(q);18.1(t);17.3(q);12.2(q)。
C) R-6-ethyl-T-10-methyl-spiral shell [4,5] last of the ten Heavenly stems-1-ketone
I) 6-ethyl-10-methyl-spiral shell [4,5] last of the ten Heavenly stems-8-alkene-1-ketone
Will be at the propylidene cyclopentanone (248g in the toluene (200g); 2mol) solution (derive from N.Katsin, R.Ikan Synth.Comm.1977,
7 (3),185) be cooled to 0 ℃.Add boron trifluoride ethyl ether complex (20ml) at 0 ℃ with the time more than 10 minutes.Dropwise add 1,3-pentadiene (the E/Z mixture that is dissolved in the toluene (200g) with the time more than 3 hours at 0 ℃ then; 345g; 5mol).Continuation was stirred 3 hours at 0 ℃.Routine operation (work-up) (on seeing) obtains crude product.Get the cycloaddition compound (yield be 51.7%) of 198.4g with the 15cmVigreux post by flash distillation, then carry out the purifying second time with 2 kinds of mixture of isomers forms.By 35cmFischer Spaltrohr
Post further distill obtain pure isomer R-6-ethyl-T-10-methyl-spiral shell [4,5] last of the ten Heavenly stems-8-alkene-1-ketone and R-6-ethyl-C-10-methyl-spiral shell [4,5] last of the ten Heavenly stems-8-alkene-1-ketone.
R-6-ethyl-T-10-methyl-spiral shell [4,5] last of the ten Heavenly stems-8-alkene-1-ketone (main isomer)
Organoleptics property: fragrance with (thujonic) smell of thujone
MS:192(M+,45);177(6);174(7);163(100);149(13);145(36);135(29);125(50);121(31);119(13);111(43);107(47);105(27);93(78);91(76);82(27);79(66);77(53);67(56%);65(27);59(10);55(41);53(32);41(60);39(46);29(26);27(33).
1H-NMR:5.62 (m, 1H); 5.55 (m, 1H); 2.38-2.02 (m, 4H); 1.94-1.75 (m, 4H); 1.60-1.48 (m, 1H); 1.32-1.20 (m, 1H); 1.12-0.87 (m, 2H); 0.91 (d and t, J=8Hz, 6H).
13C-NMR:222.2(s),130.7(d);125.3(d);55.2(s);39.6(t);35.7(d);33.8(d);29.9(t);28.5(t);23.9(t);18.2(t);17.1(q);12.2(q)。
R-6-ethyl-C-10-methyl-spiral shell [4,5] last of the ten Heavenly stems-8-alkene-1-ketone (minor isomer)
Organoleptics property: fragrance with the smell of plant
MS:192(M+,21);177(14);174(32);163(41);149(14);145(55);135(43);125(23);121(29);119(13);111(14);108(100);105(28);93(71);91(79);81(21);79(65);77(5/);67(62);65(30);59(10);55(45);53(41);41(86);39(74);29(54);27(69)。
1H-NMR:5.63(m,1H);5.34(dd,J=10Hz,2Hz,1H);2.55(m,1H);2.33-2.10(m,3H);1.95-1.70(m,5H);1.64-1.52(m,1H);1.24-1.00(m,2H);0.85(t,J=8Hz,3H);0.82(d,J=8Hz,3H)。
13C-NMR:226.6(s);131.8(d);126.0(d);55.5(s);43.0(d);40.9(t);39.3(d);28.4(t);24.4(t);24.2(t);19.7(t);16.7(q);11.9(q)。
Ii) R-6-ethyl-T-10-methyl-spiral shell [4,5] last of the ten Heavenly stems-1-ketone
With R-6-ethyl-T-10-methyl-spiral shell [4,5] last of the ten Heavenly stems-8-alkene 1-ketone (94.5%; 10g; 0.052mole) be dissolved in the ethanol (50g), at room temperature add Pd/C 5% (0.3g) also under atmospheric pressure with mixture hydrogenation.Filtering catalyst and evaporating solvent obtain the saturated ketone of crude product.In (b.p.78 ℃ in vacuum; 1.0mbar) the following compound (yield is 80.1%) that obtains pure title that distills.
MS:194(M+,10);179(6);176(20);165(58);161(3);151(8);147(25);137(22);125(87);122(53);111(100);109(57);105(15);97(15);95(67);93(20);91(21);84(16);81(71);79(33);77(19);67(54);65(10);55(36);53(16);41(29);39(13);29(7)。
1H-NMR:2.36-1.64(m,10H);1.55-1.38(m,3H);1.06-0.76(m,3H);0.91(d,J=7Hz,3H);0.87(t,J=7Hz,3H)。
13C-NMR:222.5(s);56.5(s);38.8(t);37.0(d);32.5(d);29.7(t);29.1(t);27.5(t);25.0(t);20.0(t);18.5(t);14.8(q);12.6(q)。
D) 7-methyl-spiral shell [4,5] last of the ten Heavenly stems-1-ketone and 8-methyl-spiral shell [4,5] last of the ten Heavenly stems-mixture of 1-ketone
I) 7-methyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-ketone and 8-methyl-spiral shell [4,5] last of the ten Heavenly stems-mixture of 7-alkene-1-ketone
With cyclopentanone (1310.4g; 15.6mol), isoprene (816g; 12.0mol), BHT (2.4g) and 40% formalin (the pure formaldehyde of 180.6g; 6.02mol) in the 5000 milliliters of stainless steel pressure kettle of packing into, mixture is heated to 200 ℃ kept 7 hours under stirring action.After being cooled to room temperature, reaction mixture is moved in the separating funnel.Aqueous phase discarded is washed organic phase with salt, obtain 1925g crude product cycloaddition compound.
Crude product is distilled the pure product cycloaddition of the 470g compound that obtains with mixture of isomers (ratio 35/65) form by the 15cmVigreux post.,
Yield: 47.6% (b.p.=107 ℃; 12mbar).
MS master's isomer: 164 (M+, 65); 149 (31); 146 (50); 136 (12); 135 (12); 131 (42); 121 (25); 118 (15); 108 (32); 105 (21); 93 (100); 91 (62); 79 (68); 77 (48); 68 (30); 67 (31); 65 (21); 53 (26); 41 (37); 39 (45).
1H-NMR:5.37(m,1H);1.67(s,3H);2.37-1.35(m,12H)。
Ii) 7-methyl-spiral shell [4,5] last of the ten Heavenly stems-1-ketone and 8-methyl-spiral shell [4,5] last of the ten Heavenly stems-mixture of 1-ketone
With the identical method of describing among the embodiment 3.2 from above-mentioned i) the cycloaddition compound (194g of acquisition; 1.183mol) obtaining crude mixture, yield is 85.1%.
Obtain the pure ketone of 167g99% with mixture of isomers (7/41/25/27) form by the distillation of 10cm Vigreux post.
By 35cmFischer Spaltrohr
Post distillation obtain to comprise isomer 8-methyl-spiral shell [4,5] last of the ten Heavenly stems-1-ketone (82%) and 8-methyl-spiral shell [4,5] last of the ten Heavenly stems-cut (21.6g) of 1-ketone (18%).
MS master's isomer: 166 (M+, 41); 151 (4); 148 (10); 137 (8); 133 (11); 122 (12); 110 (32); 108 (15); 97 (100); 95 (86); 93 (24); 84 (73); 81 (60); 70 (39); 68 (69); 55 (43); 53 (18); 41 (28); 39 (12).
1H-NMR;2.27(m,2H);1.96-1.68(m,6H);1.58-1.40(m,3H);1.10-1.16(m,2H);1.03-0.80(m,3H)。
13C-NMR (main isomer): 222.6 (s), 47.3 (s); 38.4 (2t); 38.1 (2t); 31.5 (t); 30.9 (d); 29.6 (t); 21.0 (q); 18.6 (t).
E) 10-ethyl-8-methyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-alcohol
I) 10-ethyl-8-methyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-ketone
Will be at the propylidene cyclopentanone (124g in the toluene (124g); 1mol) solution is cooled to 0 ℃.Add BF at 0 ℃ with the time more than 10 minutes
3Etherate (10ml).Dropwise add the isoprene (168g that is dissolved in the toluene (168g) with the time more than 3 hours at 0 ℃ then; 2.47mol).Continuation was stirred 3.5 hours at 0 ℃.Routine operation (on seeing) obtains the crude product with mixture of isomers (ratio 5/4/91) form.Obtain the pure cycloaddition compound (yield is 86%) of 165g96% with the distillation of Vigreux post.
Organoleptics property: fruity, eucalyptus and smell Salvia japonica Thunb.
MS:192(M+,19);174(31);163(77);149(20);145(100);135(25);121(14);119(26);107(45);105(24);96(31);93(47);91(51);81(31);79(39);77(35);67(26);65(17);55(25);53(21);43(15);41(38);39(31);29(20);27(26)。
1H-NMR:5.28(br?s,1H);2.40-2.31(m,1H);2.18-1.70(m,9H);1.66(br?s,3H);1.60-1.46(m,1H);1.28-0.97(m,2H);0.88(t,J=8Hz,3H)。
13C-NMR:225.2(s),133.9(s);118.2(d);52.2(s);40.1(t);39.9(d);34.8(t);33.2(t);28.3(t);24.3(t);23.3(q);19.0(t);12.0(q)。
Ii) 10-ethyl-8-methyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-alcohol
With 10-ethyl-8-methyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-ketone (14g; 0.073mol) be dissolved in the toluene (60ml), and use Vitride
In toluene (40ml) in 60~70 ℃ of reduction.Observe and find have part to transform: 22.1% ketone and 67.5% alcohol.Behind the conventional steps (on seeing), then at SiO
2On carry out column chromatography (solvent: normal hexane/MTBE:9/1) obtain with 95.6% of the form of mixture of isomers pure desired product.
MS master's isomer: 194 (M+, 3); 176 (29); 161 (10); 147 (100); 134 (12); 133 (41); 121 (17); 119 (33); 108 (17); 105 (98); 97 (20); 93 (32); 91 (32); 81 (20); 79 (22); 77 (14); 67 (17); 55 (21); 41 (21).
1H-NMR:8747:5.25(br?s,1H);3.90(m,1H);1.67(br?s,3H);1.23(m,1H,OH);2.22-1.14(m,13H);0.94(t,3H,J=7Hz)。
F) 6,8-dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-ketone and 7, the mixture of 9-dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-ketone
With cyclopentanone (1255g; 14.94mol), the 2-methyl isophthalic acid, 3-pentadiene (1000g; 12.2mol), BHT (2.3g) and 40% formalin (505g; The pure formaldehyde of 202g; 6.73mol) in the 5000ml stainless steel pressure kettle of packing into, mixture is heated to 200 ℃ kept 8 hours under stirring action.After being cooled to room temperature, aqueous phase discarded is washed organic phase with salt, obtains crude product cycloaddition compound.
It is that (b.p.=73~77 are ℃ under 1mbar for the pure product cycloaddition of the 294g compound of 4 mixture of isomers forms of 6/7/62/25 that crude product is obtained with ratio by 70cmSulzer post distillation; Yield is 24.5%).,
MS (main isomer): 178 (M+, 38); 163 (29); 160 (33); 149 (13); 145 (35); 135 (28); 122 (13); 121 (12); 119 (11); 107 (59); 105 (17); 93 (32); 91 (40); 82 (100); 79 (32); 77 (24); 67 (56); 65 (13); 55 (15); 41 (27); 39 (19).
1H-NMR (main isomer): 5.25 and 5.13 (br s, 1H); 2.44-1.80 (m, 11H); 1.67 (s, 3H); 0.89 (d, J=7Hz, 3H); 0.81 (d, J=7Hz, 3H).
13C-NMR:221.9(s);132.4(s);125.2(d);50.4(s);38.2(t);35.4(d);34.8(t);27.3(t);26.2(t);23.4(q);18.1(t);17.2(q)。
Embodiment 2
Synthesizing of compounds more of the present invention
With HP-INNOWax polyoxyethylene glycol post (30m * 0.25mm) or DB-1 methylsiloxane post (10m * 0.1mm) carry out GC to analyze.
1. the general method for preparing the strange alkali of Manny
In Virahol (50ml), stir ketone (1mol), Paraformaldehyde 96 (1mol) and Dimethylammonium chloride (1.031mol).Added the spissated HCl aqueous solution (0.6g) and reflux 30 minutes.After being cooled to room temperature, established solid filtering is removed, washed and drying with acetone.With making the solution of acquisition become alkalescence in the solid water-soluble (200ml) and by adding the 50%NaOH aqueous solution, use the ether extracting then.With salt washing bonded organic phase, and use anhydrous Na
2SO
4Dry.Filtering also, evaporating solvent obtains almost pure final compound.
The 6-[(dimethylamino) methyl]-2, the 2-dimethylcyclohexanon
Yield with 82% derives from 2, the 2-dimethylcyclohexanon.
MS:183(M+,3);95(9);69(6);58(100);41(6)。
1H-NMR:1.05(s,3H);1.21(s,3H);1.27(qd,J
q=12Hz,J
d=3.7Hz,1H);1.55(td,J
t=12Hz,J
d=3.7Hz,1H);1.66-1.93(m,4H);2.20(s,6H);2.15-2.28(m,1H);2.63-2.76(m,2H)。
The 2-[(dimethylamino) methyl]-the 4-methylcyclohexanone
Yield with 57% is also made by the 4-methylcyclohexanone with the form of mixtures of suitable/trans-isomer(ide) of 97: 3.
MS:169(M+,2);58(100)。
1H-NMR:1.01(d,J=7,3H);1.07(m,1H);1.32-1.44(m,2H);1.91-2.07(m,1H);2.18-2.30(m,2H);2.20(s,6H);2.31-2.56(m,3H);2.64(dd,J1=5Hz,J2=13Hz,1H)。
2. the general method of hot Diels-Alder reaction
To be heated to 170 ℃ (outside temperature) in high compressed steel pot at the diene (2.53mol) in the toluene (400ml), the strange alkali of Manny (0.437mol) and Resorcinol (1.4g) kept 23 hours.After being cooled to room temperature, with the 5%HCl aqueous solution and salt washing reactant.With hexanaphthene extracting water.Use anhydrous Na
2SO
4Dry bonded organic phase.By on silica gel, carry out column chromatography (elutriant: cyclohexane/ethyl acetate 19: 1) and short-path distillation subsequently (bulb-to-bulb distillation), to after filtration and the residuum that obtains behind the evaporating solvent carry out purifying.
2,2-dimethyl spiral shell [5,5] 11 carbon-8-alkene-1-ketone
Yield with 44% is by divinyl and 6-[(dimethylamino) methyl]-2, the 2-dimethylcyclohexanon makes.
B.p.=100~105℃/0.11mbar
MS:192(M+,52);177(6);149(26);135(13);120(100);107(26);94(57);79(91);67(18);55(21);41(44)。
1H-NMR:1.11(s,3H);1.13(s,3H);1.46-1.86(m,7H);1.92-2.06(m,4H);2.20-2.28(m,1H);5.55-5.67(m,2H)。
2,2,7,9-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone and 2,2,8, the mixture of 10-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone
Yield with 78% is by the 2-methyl isophthalic acid, 3-pentadiene and 6-[(dimethylamino) methyl]-2, the 2-dimethylcyclohexanon makes.GC is shown as 4 mixture of isomers with 7/8/32/53 ratio.
B.p.=120~123℃/0.043mbar
MS (main isomer): 220 (M+, 55); 205 (15); 191 (6); 177 (18); 148 (12); 135 (12); 121 (44); 107 (49); 93 (33); 82 (100); 67 (32); 41 (44).
1H-NMR:0.74-0.97(m,3H);1.05-1.20(m,7H);1.30-2.00(m,11H);2.10-2.46(m,2H);5.05-5.24(m,1H)。
2,2,7 trimethylammonium spiral shells [5,5], 11 carbon-8-alkene-1-ketone and 2,2, the mixture of 10-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-ketone
Yield with 21% is by 1,3-pentadiene and 6-[(dimethylamino) methyl]-2, the 2-dimethylcyclohexanon makes.GC is shown as 4 mixture of isomers with 5/29/32/34 ratio.
Organoleptics property: the smell of pleasant and natural juniper, pine tree, wooden and face cream, with the aftertaste of Linaool and lavender.
B.p.=52~63℃/0.18mbar
MS (main isomer): 206 (M+, 58); 191 (34); 163 (71); 147 (6); 134 (74); 121 (35); 108 (100); 93 (88); 82 (57); 67 (32); 55 (31); 41 (60).
1H-NMR:0.77-1.20(m,9H);1.33-2.48(m,11H);5.36-5.68(m,2H)。
4,7,9-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-ketone and 4,8, the mixture of 10-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-ketone
Yield with 32% is by the 2-methyl isophthalic acid, 3-pentadiene and 2-[(dimethylamino) methyl]-the 4-methylcyclohexanone makes.GC is shown as the mixture with 5 steric isomers of the ratio of 4.5/5.5/12/20/58.
Organoleptics property: wooden, the vetiveryl acetate (vetiveryl acetate) of fine multiple smell, rose and taste Syringa oblata Lindl..
B.p.=80℃/0.03mbar
MS (main isomer): 206 (M+, 53); 191 (17); 177 (18); 163 (35); 125 (18); 107 (19); 91 (22); 82 (100); 67 (28); 55 (11); 41 (13).
1H-NMR:0.74-1.20(m,7H);1.23-2.73(m,14H);5.13-5.28(m,1H)。
3. pass through the general method of hydride reduction Diels-Alder reaction affixture
To add LiAlH among cold (0 ℃) THF (600ml) at spiral shell ketone (145.6mmol) solution among the THF (150ml)
4(5.7g; 150mmol) in the slurry.Reaction is heated to room temperature, be heated to then 50 ℃ 4 hours.After being cooled to 0 ℃, add entry (6ml), the 5%NaOH aqueous solution (17ml) continuously and carefully, and then add water (6ml).Reactant at room temperature stirred until it becomes white slurries.By adding anhydrous Na
2SO
4With described slurry dried.Behind filtration and the evaporating solvent, then carry out short-path distillation.
(5RS, 6SR, 10SR)-10-ethyl-6,8-dimethyl spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-alcohol
Yield with 95% is by (10SR)-10-ethyl-6,8-dimethyl spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-ketone makes for 5RS, 6SR.GC is shown as the diastereomer of 9: 1 ratios.
Organoleptics property: the smell of xyloid, camphor, ginger
B.p.=100~105℃/0.36bars
MS:208(M+,4);190(42);175(13);161(78);148(35);133(42);125(49);119(96);105(59);91(48);82(100);67(58);55(41);41(54)。
1H-NMR:0.88-0.98(m,6H);1.05-1.10(m,1H);1.30-1.80(m,12H);1.85-2.00(m,2H);2.16-2.27(m,1H);3.91-3.97(m,1H);5.15-5.19(m,1H)。
R-6-ethyl-T-10-methyl-spiral shell [4,5] last of the ten Heavenly stems-1-alcohol
Yield with 88% is made by R-6-ethyl-T-10-methylspiro [4,5] last of the ten Heavenly stems-1-ketone.Isomer proportion (drawing): 78/8/5 by GC.Organoleptics property: the smell of Wrinkled Gianthyssop Herb, borneol and camphor
B.p.=102℃/1.7mbarMS:196(M+,17);167(18);149(100);123(63);107(20);95(60);81(54);67(47);55(59);41(68)。
1H-NMR:0.80-1.10(m,2H);0.89(t,J=7.1Hz,3H);0.98(d,J=7.1Hz,3H);1.29-1.84(m,13H);1.97-2.05(m,1H);3.87-3.94(m,1H)。
6,8-dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-is pure and mild 7, the mixture of 9-dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-alcohol
Yield with 99% is by 6, and in 8-dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-ketone and 7, the mixture of 9-dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-ketone makes.GC shows that the ratio of isomer is 10/21/63.
B.p.=95℃/0.12mbar
MS (main isomer): 180 (M
+, 6); 162 (77); 147 (87); 134 (86); 119 (50); 105 (98); 91 (90); 82 (100); 67 (100); 55 (48); 41 (91).
1H-NMR:0.86-1.15(m,3H);1.22-2.30(m,15H);3.65-3.99(m,1H);5.19-5.46(m,1H)。
4. the general method of the esterification of volution alcohol
Acetyl Chloride 98Min. (215.4mmol) slowly is added in dried CH
2Cl
2In ethanol (600ml) (134.6mmol), pyridine (228.8mmol) and Dimethylamino pyridine (27mmol) solution.After at room temperature stirring 5 hours, the vaporising under vacuum solvent.Residuum is dissolved in the pentane and water, saturated NaHCO
3The aqueous solution, 10%CuSO
4The aqueous solution and salt washing mixture.Use anhydrous Na
2SO
4Dry organic phase.Behind filtration and the evaporating solvent, with short-path distillation purifying residuum.
Perhaps, can carry out esterification according to following method:
(12.22mmol) joins at CH with diacetyl oxide
2Cl
2In ethanol (15ml) (6.11mmol), pyridine (13.44mmol) and Dimethylamino pyridine (0.61mmol) solution.At room temperature reaction stirred is 4 hours, concentrates under vacuum then.With short-path distillation purifying residuum.
R-6-ethyl-T-10-methyl-spiral shell [4,5] last of the ten Heavenly stems-1-base acetic ester
Yield with 62% is made by R-6-ethyl-T-10-methyl-spiral shell [4,5] last of the ten Heavenly stems-1-alcohol.
Organoleptics property: very graceful wooden, caryophyllene, vetiveryl acetate (vetiveryl acetate) and slight santal smell, with the interior perfume (or spice) of amber and camphor.
B.p=70℃/0.15mbar
MS:238(M
+,1);209(4);178(16);163(13);149(100);135(8);123(21);107(17);95(29);81(28);67(25);43(67);41(29)。
1H-NMR:0.87(d,J=6.7Hz,3H);0.91(t,J=7.3Hz,3H);0.97-1.10(m,2H);1.30-1.80(m,13H);2.04(s,3H);2.13-2.20(m,1H);4.88(t,J=7.3Hz,1H)。
6,8-dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-base acetic ester and 7, the mixture of 9-dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-base acetic ester
Yield with 99% is pure and mild 7 by 6,8 dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-, and the mixture of 9-dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-alcohol makes.The GC ratio of isomer is 13/8/75.
B.p=70℃/0.06mbar
MS (main isomer): 222 (M+, 1); 180 (5); 162 (48); 147 (53); 134 (70); 119 (37); 105 (43); 91 (37); 82 (53); 67 (43); 43 (100); 41 (36).
1H-NMR:0.82-1.20(m,3H);1.32-2.27(m,19H)。
(5RS, 6SR, 10SR)-10-ethyl-6,8 dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-base acetic ester
Yield with 97% by (5RS, 6SR, 10SR)-10-ethyl-6,8 dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-alcohol makes.GC shows that the ratio of isomer is 4.5/85.1/8.4.
Organoleptics property: great wooden, vetiveryl acetate sesquiterpene smell.
B.p=78~83℃/0.078mbar
MS:250(M+,1);190(72);175(25);161(100);148(55);134(37);126(24);119(43);108(29);93(28);82(41);67(19);43(12)。
1H-NMR:0.89(d,J=7.5Hz,3H);0.94(t,J=7.3Hz,3H);0.97-1.15(m,1H);1.38-1.45(m,1H);1.51-1.81(m,8H);1.61(broads,3H);1.91-2.11(m,2H);2.03(s,3H);4.87(t,J=6Hz,1H);5.14-5.17(m,1H)。
5. pass through the general method of MeLi alkanisation Diels-Alder reaction affixture
(1.6M, 40ml is 64mmol) in the MeLi solution in will to be added in dried diethyl ether at spirocyclic ketone (43mmol) solution in the dried diethyl ether (30ml) at-78 ℃.Heat reactant to room temperature and stir and to spend the night.After being cooled to 0 ℃, adding entry and use ether extracting mixture.Also use solid Na with salt washing bonded organic phase
2SO
4Dry.Behind filtration and the evaporating solvent, on silica gel, carry out column chromatography (elutriant: cyclohexane/ethyl acetate 29: 1) and by short-path distillation product is carried out purifying.
1,6,8-trimethylammonium-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-is pure and mild 1,7, the mixture of 9-trimethylammonium-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-alcohol
Yield with 40% is by 6,8 dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-ketone and 7, and the mixture of 9-dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-ketone makes.The GC ratio of isomer is 4/4/4/5/6/74.
Organoleptics property: the smell of borneol, camphor and Wrinkled Gianthyssop Herb.
B.p.=68℃/0.04mbar
MS (main isomer): 194 (M
+, 7); 176 (29); 161 (28); 147 (11); 136 (46); 121 (40); 119 (40); 107 (38); 105 (39); 93 (40); 91 (41); 82 (58); 67 (43); 55 (20); 43 (100).
1H-NMR:1.07(d,J=7.1Hz,3H);1.27(s,3H);1.35-2.13(m,12H);1.61(s,3H);5.34-5.38(m,1H)。
Embodiment 3
Synthesizing of compounds more of the present invention
According to J.T.A.Reuvers, A de Groot, ethylidene-dimethylcyclohexanon that Synthesis 1982,1105 obtains with the form of mixtures of E/Z isomer (87/13).
1. the general method of hot Diels-Alder reaction
Ethylidene-dimethylcyclohexanon and 3 normal diene, 200 ℃ of heating 18h in pressure kettle with 5g (32.8mmol).Cooling is also removed polymer by short-path distillation, by flash chromatography (pentane/ether=99/1) and short-path distillation purifying spirocyclic ketone.
2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-ketone
Yield with 51% is made by ethylidene-dimethylcyclohexanon and divinyl, and is the form of 2 mixture of isomers of 13/1 with ratio.
Organoleptics property: camphor
MS:206(M+,68);134(75);93(100);79(83);41(91)。
1H-NMR (main isomer): 0.73 (d, J=7,3H); 1.08 (s, 3H); 1.10 (s, 3H); 1.50-1.85 (m, 7H); 1.97 (m, 2H); 2.22 (m, 1H); 2.33 (sept.:J=7,1H); 5.51 (m, 1H); 5.65 (m, 1H).
2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone
Yield with 90% is made by ethylidene-dimethylcyclohexanon and isoprene, and is the form of 2 mixture of isomers of 2/3 with ratio.These 2 isomer can separate by the preparation GC on Supelcowax-10 post (30m * 0.53mm, 2 μ filter membranes).
Organoleptics property: very natural fragrance, green and fruit aroma, with the aftertaste of argy wormwood and ginger.
Minor isomer:
MS:220(M+,48);192(43);135(48);122(65);107(100);93(59);79(38);67(31);55(42);41(78)。
1H-NMR(C
6D
6):0.74(d,J=7,3H);1.01(s,3H);1.12(s,3H);1.30-1.85(m,8H);1.53(large?s,3H);1.96(d,J=16,1H);2.09(d,J=16,1H);2.52(sept.:J=7,1H);5.32(m,1H)。
Main isomer:
MS:220(M+,67);148(29);121(51);107(100);93(61);82(69);67(35);55(43);41(82)。
1H-NMR(C
6D
6):0.75(d,J=7,3H);0.99(s,3H);1.12(s,3H);1.25-1.75(m,8H);1.56(large?s,3H);2.07(m,2H);2.57(sept.:J=7,1H);5.13(m,1H)。
2,2,7,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone
Yield with 32% is made by ethylidene-dimethylcyclohexanon and m-pentadiene, and is the form of 2 mixture of isomers of 1/1 with ratio.These 2 steric isomers can separate by the preparation GC on Supelcowax-10 post (30m * 0.53mm, 2 μ filter membranes).
Organoleptics property: wooden, pine tree and aromatic odour.
First elution peak:
MS:220(M+,98);153(93);107(100);93(64);68(26);55(18);41(22)。
1H-NMR:0.73(d,J=7,3H);0.79(d,J=7,3H);1.06(s,3H);1.11(s,3H);1.50-1.98(m,8H);2.33(sept.:J=7,1H);2.44(m,1H);5.53(m,2H)。
Second elution peak:
MS:220(M+,50);205(100);148(46);121(35);107(80);93(42);82(48);69(16);42(23)。
1H-NMR:0.77(d,J=7,3H);0.90(d,J=7,3H);1.13(s,6H);1.41-1.98(m,8H);2.07(sept.:J=7,1H);2.73(m,1H);5.29(m,1H);5.60(m,1H)。
Under-20 ℃, at 1 normal AlCl
3Carry out identical reaction in the toluene under existing,, obtain same isomer mixture, but the isomer proportion after distillation is 7: 1, yield is 75%.
2. spirocyclic ketone hydrogenant general method
In the presence of 100mg 5%Pd/C, the hydrogenation under 20 ℃ and normal atmosphere of the mixture of spirocyclic ketone (0.1mole) that will be in 200mlEtOH.When absorbing 1 equivalent H
2After, filtering mixt on diatomite, vacuum concentration and by the short-path distillation purifying.
2,2,7-trimethylammonium spiral shell [5,5] 11 carbon-1-ketone
By 2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-ketone makes with quantitative yield, and is the form of 2 mixture of isomers of 13/1 with ratio.
MS (main isomer): 208 (M+, 62); 136 (42); 126 (94); 109 (56); 95 (92); 81 (92); 67 (75); 55 (71); 41 (100).
1H-NMR (main isomer): 0.66 (d, J=7,3H); 1.06 (s, 3H); 1.10 (s, 3H); 1.14-1.92 (m, 14H); 2.19 (m, 1H).
2,2,7,11-tetramethyl-spiral shell [5,5] 11 carbon-1-ketone
Yield with 83% is by 2,2,7, and 11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone makes, and (pentane/ether=98/2) is the form of 2 mixture of isomers of 7/1 with ratio behind chromatography.
MS (main isomer): 222 (M+, 30); 153 (38); 109 (100); 95 (57); 81 (39); 69 (39); 55 (43); 41 (57).
1H-NMR MS (main isomer): 0.64 (d:J=7,3H); 0.81 (d:J=7,3H); 1.05 (s, 3H); 1.10 (s, 3H); 1.29-1.93 (m, 11H); 2.03 (s, 1H); 2.16 (s, 1H); 2.35 (s, 1H).
3. use LiAlH
4The general method of reduction spirocyclic ketone
To add LiAlH among cold (0 ℃) THF (600ml) at spiral shell ketone (145.6mmol) solution among the THF (150ml)
4(5.7g; 150mmol) in the slurry.Reaction is heated to room temperature, be heated to 50 ℃ then and kept 4 hours.After being cooled to 0 ℃, add entry (6ml), the 5%NaOH aqueous solution (17ml) continuously and carefully, and then add water (6ml).Reactant at room temperature stirred until it becomes white slurries.By adding anhydrous Na
2SO
4With described slurry dried.Filter also and carry out short-path distillation after the evaporating solvent.
2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-alcohol
Yield with 94% is by 2,2, and 11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-ketone makes, and is the form of 3 mixture of isomers of 7/1/1 with ratio.
MS (main isomer): 208 (M+, 22); 190 (40); 105 (80); 93 (100); 79 (38); 69 (19); 55 (21); 41 (17).
1H-NMR (main isomer): 0.87 (d, J=7,3H); 1.03 (s, 6H); 1.12-1.53 (m, 7H); 1.71 (m, 1H); 1.90 (m, 1H); 2.10 (m, 1H); 2.25 (m, 1H); 3.29 (d, J=4,1H; Because D
2The adding of O is transformed into s); 5.68 (m, 2H).
2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-alcohol
Yield with 74% is by 2,2,9, and 11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone makes, and is the form of 2 mixture of isomers of 2.3/1 with ratio.These 2 isomer can be under 120~240 ℃, by (GC on the 30m * 0.25mm) separates at the Carbowax post.
MS (first elution peak): 222 (M+, 12); 204 (32); 119 (72); 107 (100); 93 (31); 79 (21); 67 (28); 55 (40); 41 (59).
MS (second elution peak): 222 (M+, 3); 204 (12); 119 (35); 107 (100); 91 (23); 79 (14); 676 (16); 55 (27); 41 (38).
1H-NMR:0.80-0.86 (m, 3H); 0.97-1.05 (m, 6H); 1.07-1.24 (m, 3H); 1.11-1.60 (m, 5H); 1.64 (s large, 3H), 1.80-2.06 (m, 2H); 2.16-2.32 (m, 1H); 6.61 (m, 1H); 3.25 (d, J=4,1h; Because D
2The adding of O is transformed into s), 5.38 (m, 1H).
2,2,7-trimethylammonium spiral shell [5,5] 11 carbon-1-alcohol
(SiO behind chromatography
2, elutriant: pentane/ether=9/1) with 85% yield by 2,2,7-trimethylammonium spiral shell [5,5] 11 carbon-1-ketone makes, and is the form of 2 mixture of isomers of 1/1 with ratio.These 2 isomer can be under 120~240 ℃, by (GC on the 30m * 0.25mm) separates at the SPB-1 post.
MS (first elution peak): 210 (M+, 85); 122 (52); 109 (65); 96 (78); 82 (100); 67 (40); 55 (45); 41 (29).
MS (second elution peak): 210 (M+, 60); 122 (62); 109 (81); 96 (86); 82 (100); 67 (48); 55 (55); 41 (35).
1H-NMR:0.82 and 0.89 (d, J=7,3H); 0.93,0.98,1.02 and 1.07 (s, 6H); 1.10-2.22 (m, 15H); 3.30 and 3.63 (d, J=6 is by D
2The adding of O is transformed into s, 1H).
2,2,7,11-tetramethyl-spiral shell [5,5] 11 carbon-1-alcohol
By 2,2,7,11-tetramethyl-spiral shell [5,5] 11 carbon-1-ketone makes with quantitative yield, and is the form of 3 mixture of isomers of 1/16/2 with ratio.
Organoleptics property: natural woody odor, with the intension and the terpenic aftertaste of China fir, Atlas cedar type.
MS (main isomer): 224 (M+, 48); 123 (23); 109 (100); 95 (58); 82 (40); 69 (28); 55 (29); 41 (20).
1H-NMR (main isomer): 0.83 (d, J=7,3H); 0.97 (s, 3H); 1.06 (s, 3H); 1.22 (d, J=7,3H); 1.10-1.93 (m, 13H); 2.17 (m, 1H); 2.35 (m, 1H); 3.37 (d, J=5,1H; By D
2The adding of O is transformed into s,, 1H).
4. the general method of pure esterification
In volution alcohol (1 equivalent) solution in pyridine (1000% weight meter), add diacetyl oxide (10 equivalent), and mixture is finished (GC) 115 ℃ of heating until reaction.After the cooling, with ether extracting residuum, water, the 10%HCl aqueous solution, saturated NaHCO successively
3With the salt washing, use Na then
2SO
4Drying is also carried out vacuum concentration.By flash chromatography (SiO
2On, elutriant: pentane/ether=95/5) and short-path distillation the crude product acetic ester is carried out purifying.
2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester
Yield with 58% is by 2,2, and 11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-alcohol makes, and is the form of 3 mixture of isomers of 7/1/1 with ratio.
Organoleptics property: the smell of wooden, amber/grane ambra and China fir type.
MS (main isomer): 250 (M+, 0); 190 (99); 105 (100); 93 (66); 79 (31); 69 (16); 55 (18); 43 (37).
1H-NMR (main isomer): 0.86 (d, J=7,3H); 0.96 (s, 6H); 1.15-1.70 (m, 8H); 1.82 (m, 1H); 2.20 (s, 3H); 2.18 (m, 1H); 2.53 (m, 1H); 4.78 (s, 1H); 5.50 (m, 1H); 5.58 (m, 1H).
2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester
By 2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-alcohol makes with quantitative yield, and is the form of 2 mixture of isomers of 2.3/1 with ratio.
MS (minor isomer): 264 (M+, 0); 204 (47); 119 (80); 107 (79); 91 (34); 79 (21); 67 (21); 55 (35); 43 (100).
MS (main isomer): 264 (M+, 0); 204 (46); 119 (100); 107 (49); 91 (23); 79 (19); 67 (19); 55 (27); 43 (86).
1H-NMR:0.79-0.86 (m, 3H); 0.94 (s, 3H); 0.98 (s, 3H); 1.17-1.86 (m, 8H); 1.63 (s large, 3H); 1.98 and 1.99 (s, 3H); 2.04-2.17 (m, 2H); 2.48 (m, 1H); 4.72 and 4.75 (s, 1H); 5.19 and 5.29 (m, 1H).
5. the general method of volution alcohol etherificate
7-methoxyl group-3,5,8,8-tetramethyl-spiral shell [5,5] 11 carbon-2-alkene
At room temperature in the mixture of the KH30% that does the 0.36g (2.7mmole) among the THF at oily and 4ml, add 2,2,9 among the dried THF of 0.5g (2.25mmole) at 2ml, 11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-alcoholic solution.Under 25 ℃, after 45 minutes, add the CH of 0.96g (6.67mmole)
3I stirs mixture 1 hour at 25 ℃, pours in the ice, uses the ether extracting, salt washing, Na
2SO
4Dry also vacuum concentration.Obtain the pure volution ether of 0.55g (99%) and be the form of 2 mixture of isomers of 2.3/1 with ratio by short-path distillation purifying crude product.
Organoleptics property: fine woody odor, with Vetiveria zizanoides (vetyver), fragrance and taste cistus creticus.
MS (main isomer): 236 (M+, 11); 204 (46); 119 (85); 107 (100); 93 (41); 79 (26); 67 (24); 55 (38); 41 (58).
MS (minor isomer): 236 (M+, 6); 204 (30); 119 (40); 107 (100); 91 (28); 79 (18); 67 (15); 55 (26); 41 (37).
1H-NMR:0.78-0.85 (m, 3H); 0.98 and 0.99 (s, 6H); 1.04-2.26 (m, 13H); 2.52 (m, 1H); 2.74 (m, 1H); 3.44 and 3.46 (s, 3H); 5.26 and 5.32 (m, 1H).
Embodiment 4
According to synthesizing of some compound of the present invention
A) 1,2, the preparation of 2-trimethylammonium spiral shell [5,5] 11 carbon-1-alcohol
I) 1,2,2-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene 1-alcohol
(embodiment 2, and step 5) is with 2, and 2-dimethyl spiral shell [5,5] 11 carbon-8-alkene 1-ketone is handled with lithium methide and obtained 1,2,2-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene 1-alcohol, yield 98% according to usual method.By short-path distillation purifying crude product.(B.p.=140~150℃/0.032mbar)
Organoleptics property: wooden, China fir smell
MS:208(M+,16);190(41);175(42);147(86);123(44);106(100);91(72);79(74);67(43).
1H-NMR:0.97-1.17(m,9H);1.20-2.35(m,13H);5.50-5.70(m,2H).
Ii) 1,2,2-trimethylammonium spiral shell [5,5] 11 carbon-1-alcohol
According to general method (embodiment 3, step 2) with i) product that obtains carries out hydrogenation, obtains the compound of title with 96% yield.By short-path distillation purifying crude product.(B.p.=80~85℃/0.064mbar)
Organoleptics property: wooden and soil ulmin smell, with the intension of Wrinkled Gianthyssop Herb and amber.
MS (main isomer): 210 (M+, 18); 192 (17); 177 (31); 149 (100); 136 (25); 126 (41); 122 (45); 109 (43); 96 (46); 82 (82); 67 (42); 55 (36).
1H-NMR:0.96(s,3H);1.00(s,3H);1.12(s,3H);1.05-1.65(m,15H);1.85-1.95(m,2H)。
B) preparation of 7-ethyl-11-methylspiro [5,5]-1-undecyl acetic ester
(embodiment 2, and step 4) is carried out acetylize with 7-ethyl-11-methylspiro [5,5] 11 carbon-1-alcohol, with the title compound of 91% yield acquisition with the mixture of isomers form according to general method.By short-path distillation purifying crude product.(B.p.=81℃/0.025mbar)
Organoleptics property: wooden, terpenes smell.
MS (main isomer): 252 (M+, 15); 223 (45); 192 (29); 163 (100); 123 (65); 107 (23); 95 (55); 81 (45); 67 (26).
1H-NMR:0.80-1.95(m,23H);1.90-2.05(m,4H);4.90-5.45(m,1H)。
C) 1-ethyl-7-methoxyl group-undecanoic preparation of 5-methylspiro [5,5]
I) 11-ethyl-7-methylspiro [5,5] 11 carbon-8-alkene-1-alcohol
(embodiment 2, step 3) LiAlH according to general method
4With the reduction of 11-ethyl-7-methylspiro [5,5] 11 carbon-8-alkene-1-ketone, make title compound with 4: 1 mixture of isomers form with 92% yield.By short-path distillation purifying crude product.(B.p.=102℃/0.03mbar)
Organoleptics property: woody odor.
MS (main isomer): 208 (M+, 3); 190 (36); 179 (26); 161 (51); 139 (46); 121 (46); 111 (100); 105 (44); 93 (60); 81 (34); 67 (27).
1H-NMR:0.85-1.10(m,8H);1.25-2.55(m,13H);3.75(m,1H);5.52(m,2H)。
Ii) 5-ethyl-7-methoxyl group-1-methylspiro [5,5] 11 carbon-2-alkene
11-ethyl-7-methylspiro [5,5] the 11 carbon-8-alkene-1-alcohol that obtains according to general method (embodiment 3, and step 5) is with i) methylates, and makes the compound of title of 2.5: 1 isomer mixture with 95% yield.By short-path distillation purifying crude product.(B.p.=80℃/0.033mbar)
Organoleptics property: eucalyptus and aromatic odour.
MS (main isomer): 222 (M+, 8); 193 (24); 190 (63); 161 (55); 153 (36); 125 (80); 105 (100); 93 (67); 79 (26); 67 (19).
1H-NMR:0.82-1.12(m,8H);1.15-2.50(m,12H);3.12-3.30(m,4H)。
Iii) 1-ethyl-7-methoxyl group-5-methylspiro [5,5] undecane
5-ethyl-7-methoxyl group-1-methylspiro [5,5] the 11 carbon-2-alkene that will ii) obtain according to general method (embodiment 3, step 2) carries out hydrogenation, obtains the compound of title with 93% yield.By short-path distillation purifying crude product.(B.p.=80℃/0.029mbar)
Organoleptics property: pine, camphor smell.
MS (main isomer): 224 (M+, 55); 163 (100); 123 (57); 95 (64); 81 (43); 71 (25); 67 (23).
1H-NMR:0.82-1.05(m,8H);1.12-1.90(m,16H);3.15-3.35(m,4H)。
D) 1, the preparation of 8-dimethyl spiral shell [4 5] last of the ten Heavenly stems-1-alcohol
According to general method (embodiment 2, step 5) with 7-methylspiro [4,5] last of the ten Heavenly stems-1-ketone and 8-methylspiro [4,5] last of the ten Heavenly stems-mixture one of 1-ketone and lithium methide reacts, and makes the compound of title with 43% yield.By the column chromatography on the silica gel (elutriant: cyclohexane/ethyl acetate 29: 1) and short-path distillation come the purifying crude product.(B.p.=68℃/0.04mbar)
Organoleptics property: wooden, camphor, wine cellar smell.
MS (main isomer): 182 (M+, 0.5); 167 (30); 164 (17); 139 (13); 135 (41); 122 (32); 108 (36); 95 (26); 93 (37); 81 (30); 79 (25); 71 (55); 43 (100).
1H-NMR:0.98(d,J=7Hz,3H);s,3H);1.20-1.90(m,16H)。
E) 6-ethyl-1-methoxyl group-8-methylspiro [4,5] decane
I) 10-ethyl-1-methoxyl group-8-methylspiro [4,5] last of the ten Heavenly stems-7-alkene
(embodiment 3, and step 5) is carried out oxygen-methylate (O-methylated) with sodium hydride and methyl-iodide with 10-ethyl-8-methylspiro [4,5] last of the ten Heavenly stems-7-alkene-1-alcohol, make title compound with the mixture of isomers form with 93% yield according to general method.By short-path distillation purifying crude product.(B.p.=80℃/0.04mbar)
MS (main isomer): 208 (M+, 3); 176 (47); 147 (100); 133 (30); 119 (25); 105 (90); 93 (34); 91 (41).
1H-NMR:0.85-0.98(m,3H);1.05-2.20(m,16H);3.10-3.60(m,4H);5.15-5.60(m,1H)。
Ii) 6-ethyl-1-methoxyl group-8-methylspiro [4,5] decane
With 87% yield the methyl ether that A prepares is carried out hydrogenation according to general method (embodiment 3, step 2), make compound with the title of isomer mixture form.By short-path distillation purifying crude product.(B.p.=80℃/0.1mbar)
Organoleptics property: wooden and China fir smell.
MS (main isomer): 210 (M+, 15); 149 (100); 123 (12); 107 (15); 93 (20); 81 (27).
1H-NMR:0.80-0.90(m,6H);0.95-2.10(m,16H);3.15-3.65(m,4H)。
F) 2,6,8/2,7, the preparation of 9-trimethylammonium spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-alcohol
(embodiment 2, step 3) LiAlH according to general method
4With 2,6,8 and 2,7, in 9-trimethylammonium spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-ketone reduction, obtain title compound with the mixture of isomers form with 87% yield.By short-path distillation purifying crude product.(B.p.=82℃/0.02mbar)
Organoleptics property: wooden, Moschus, argillous smell, with tonalide (tonalide) and cashmere keynote and fennel and fruit taste.
MS (main isomer): 194 (M+, 2); 176 (57); 161 (69); 148 (100); 134 (21); 133 (23); 121 (73); 119 (49); 105 (54); 91 (35); 82 (39); 67 (31).
1H-NMR:0.85-1.20(m,7H);1.25-2.20(m,13H);3.28(m,1H);5.05-5.55(m,1H)。
Embodiment 5
Synthesizing of some compounds of the present invention
A) (1RS, 6SR, 11SR)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester and (1RS 6RS, 11RS)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester
I) (6RS, 11RS)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone
Under 0 ℃, to the AlCl of the 6.7g (0.05mole) in toluene (200ml)
3Mixture in dropwise add ethylidene-dimethylcyclohexanon of 152.2g (1mole) with the time more than 50 minutes.0 ℃ after following 30 minutes, dropwise add the isoprene of 70g (1.1mole) with the time more than 30 minutes.0 ℃ after 1 hour, mixture poured in the 200g trash ice and with ether extracting 2 times.Use saturated NaHCO
3Wash organic phase, wash with water 2 times and use Na
2SO
4Drying concentrates the spirocyclic ketone with 2 main isomer (ratio 9: 1) form that also obtains 195g (yield=88%) with drying with the distillation of Vigreux equipment.These 2 isomer can separate by the preparation GC on Supelcowax-10 post (30m * 0.53mm, 2 μ filter membranes).
(6RS, 11RS)-2,2,8,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone (minor isomer)
1H-NMR(C
6D
6):0.74(d,J=7,3H);1.01(s,3H);1.12(s,3H);1.30-1.85(m,8H);1.53(1arge?s,3H);1.96(d,J=16,1H);2.09(d,J=16,1H);2.52(sedt.:J=7,1H);5.32(m,1H)。
MS:220(M+,48);192(43);135(48);122(65);107(100);93(59);79(38);67(31);55(42);41(78)。
(6RS, 11RS)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-5-ketone (main isomer)
1H-NMR(C
6D
6):0.75(d,J=7,3H);0.99(s,3H);1.12(s,3H);1.25-1.75(m,8H);1.56(large?s,3H);2.07(m,2H);2.57(sept.:J=7,1H);5.13(m,1H)。
MS:220(M+,67);148(29);121(51);107(100);93(61);82(69);67(35);55(43);41(82)。
Ii) (1RS, 6SR, 11SR)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-pure and mild (1RS, 6RS, 11RS)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-alcohol
The general method of describing in Application Example 3, the step 3, with (6RS, 11RS)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone obtains 2 alcohol with 3: 1 ratios as initial compounds, by using these 2 alcohol of 30cmFischer post fractionation by distillation.
(1RS, 6SR, 11SR)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-alcohol (main isomer)
B.p.
(0.1mbar)=140℃
1H-NMR:0.85(d,J=7,3H);1.01(s,3H);1.03(s,3H);1.65(s,3H);1.90(m,1H);2.02(m,1H);2.28(m,1H);2.62(m,1H);3.26(d,J=3,1H);5.35(m,1H)。
MS:222(M+,16);204(43);134(20);119(71);107(100);93(33);82(25);69(29);55(40);41(55)。
(1RS, 6RS, 11RS)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-alcohol (minor isomer)
B.p.
(0.7mbar)=129℃
1H-NMR:0.89(d,J=7,3H);0.92(s,3H);0.98(s,3H);1.60(s,3H);2.02(m,2H);2.12(m,1H);3.35(d,J=5.5,1H);5.23(m,1H).
MS:222(M+,2);204(55);134(30);119(100);107(63);93(31);79(21);67(25);55(37);41(47).
Iii) (1RS, 6SR, 11SR)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester and (1RS, 6RS, 11RS)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester
The general method of describing in Application Example 3, the step 4, with quantitative yield by (1RS, 6SR, 11SR)-2,2,9, and 11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-alcohol acquisition (1RS, 6SR, 11SR)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester.
1H-NMR:0.83(d,J=7,3H);0.94(s,3H);0.96(s,3H);1.63(s,3H);1.80(m,1H);1.98(s,3H);2.11(m,2H);2.49(m,1H);4.75(s,1H);5.20(m,1H)。
MS:264(M+,0);204(59);134(21);119(100);107(47);93(23);79(15);67(15);55(25);43(83)。
By (1RS, 6RS, 11RS)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-alcohol with quantitative yield obtain (1RS, 6RS, 11RS)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester.
1H-NMR:0.85(s,3H);0.92(d,J=7,3H);0.96(s,3H);1.59(s,3H);2.06(s,3H);2.17(m,2H);4.86(s,1H);5.22(s,1H)。
MS:264(M+,0);204(65);134(32);119(100);107(62);93(26);79(16);67(18);27(55);43(94)。
B) (1RS, 6RS, 11RS)-2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-alcohol
I) (6RS, 11RS)-2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-ketone
With the identical method of describing in the present embodiment, at a.i) the basis on replace isoprene with divinyl, obtain title compound, purity>99% (not having the visible diastereomer) with 83% yield.Physical spectrum and embodiment 3, describe in the step 12,2,11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-ketone is identical.
Ii) (1RS, 6SR, 11SR)-2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-pure and mild (1RS, 6RS, 11RS)-2,2,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-alcohol
The general method of describing in Application Example 3, the step 3 use i) the ketone acquisition that obtains is with 2 alcohol of 85/15 ratio, separates by the preparation GC on Supelcowax-10 post (30m * 0.53mm, 2 μ filter membranes).
(1RS, 6SR, 11SR)-2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-alcohol (main isomer)
Spectrum and embodiment 3, that describes in the step 3 is identical
(1RS, 6RS, 11RS)-2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-alcohol (minor isomer)
1H-NMR:0.89(d,J=7,3H);0.93(s,3H);0.99(s,3H);1.74(m,1H);1.90(m,1H);2.03(m,2H);2.18(m,1H);3.36(d,J=5,1H);5.56(m,2H)。
MS:208(M+,1);190(47);147(32);120(30);105(100);93(79);79(36);69(23);55(31);41(29)。
C) 7-ethyl-11-methylspiro [5,5] 11 carbon-1-alcohol
I) 11-ethyl-7-methylspiro [5,5] 11 carbon-8-alkene-1-ketone
According to ai) in method, in the presence of aluminum chloride, (E)-propylidene pimelinketone and isoprene one are reacted, obtain title product with 76% yield with the mixture of isomers of 4: 1 ratios.Crude product is used for following step.
Organoleptics property: aromatic odour
MS (main isomer): 206 (M+, 67); 191 (16); 177 (100); 149 (28); 139 (62); 125 (36); 108 (58); 93 (68); 79 (27); 67 (30).
1H-NMR:0.72-0.98(m,6H);1.42-2.52(m,14H);5.25-5.62(m,2H)。
Ii) 11-ethyl-7-methylspiro [5,5] 11 carbon-1-ketone
According to general method (embodiment 3, step 2) with i) in the cycloaddition thing hydrogenation that obtains, obtain with 92% yield, with the title compound of 3: 1 isomer mixture forms.By (B.p.=102 ℃/0.03mbar) purifying crude product of short-path distillation.
MS (main isomer): 208 (M+, 47); 190 (21); 179 (82); 161 (20); 151 (31); 139 (68); 125 (100); 109 (35); 95 (74); 81 (57); 67 (41); 55 (36).
1H-NMR:0.72-0.98(m,7H);1.03-2.35(m,17H)。
Iii) 7-ethyl-11-methylspiro [5,5] 11 carbon-1-ketone
(embodiment 2, and step 3) has LiAlH with the ii) middle product that obtains according to general method
4Promoted (LiAlH
4-mediated) reduction reaction obtains compound with the title of isomer mixture form with 88% yield.By (B.p.=80 ℃/0.033mbar) crude product is carried out purifying of short-path distillation.
Organoleptics property: the smell of a kind of natural wooden, China fir, agar and Moschus
MS (main isomer): 210 (M+, 65); 181 (37); 163 (76); 139 (20); 123 (84); 109 (23); 95 (100); 81 (68); 67 (39); 55 (45).
1H-NMR:0.72-1.00(m,5H);1.05-2.35(m,20H);3.70-4.20(m,1H)。
Embodiment 6
2,2,6,8 and 2,2,7, the preparation of the mixture of 9-tetramethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-alcohol
I) 2,6,8 and 2,7, the mixture of 9-trimethylammonium spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-ketone
With the N-butyllithium (1.6M in normal hexane, 172ml, 0.275mol) be added in diisopropyl amine solution among the THF (300ml) (30.4g, 0.3mol) in, keep internal temperature about-40 ℃.Add DMPU (1,3-dimethyl-3,4,5,6-tetrahydrochysene-2 (1H)-pyrimidone) (38.4g, 0.3mol), then, after 15 minutes, with 30 minutes times adding 6,8 and 7, the mixture of 9-dimethyl spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-ketone (44.74g, 0.25mol).After stirring more than 30 minute, add fast methyl-iodide (106g, 0.75mol).After 15 minutes, reactant is heated fast to 0 ℃.(18.6g 0.31mol) and with reactant heats to room temperature to add acetic acid.Pentane extracting 2 times are also used in reactant water (500ml) quenching.With each organic phase part water, NaHSO successively
3The aqueous solution, saturated NaHCO
3The aqueous solution and brine treatment.Use Na
2SO
4Dry bonded organic phase part, with filter and evaporating solvent after the liquid that obtains with (B.p.=105 ℃/0.47mbar) carry out purifying of short-path distillation.Obtain the title product with the mixture of isomers form (42.85g, yield=89%) of colourless liquid shape.
Organoleptics property: smell fragrance, camphor and eucalyptus.
MS (main isomer): 192 (M+, 59); 177 (39); 174 (24); 163 (15); 159 (36); 149 (28); 122 (29); 107 (87); 93 (34); 91 (40); 82 (100); 67 (33).
1H-NMR:0.72-1.05(m,3H);1.05-1.15(m,3H);1.20-2.85(m,13H);5.08-5.35(m,1H)。
Ii) 2,2,6,8 and 2,2,7, the mixture of 9-tetramethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-ketone
With identical method from i) in the product that obtains preparation with the title compound of mixture of isomers form.Yield is 86%.By (B.p.=88 ℃/0.51mbar) purifying crude product of short-path distillation.
Organoleptics property: smell fragrance, camphor and sawdust.
MS (main isomer): 206 (M+, 29); 191 (36); 188 (20); 173 (16); 163 (14); 122 (54); 107 (100); 93 (24); 91 (26); 82 (30); 79 (17).
1H-NMR:0.75-1.30(m,9H);1.50-2.55(m,12H);5.10-5.30(m,1H)。
Iii) 2,2,6,8 and 2,2,7, the mixture of 9-tetramethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-alcohol
(embodiment 2, and step 3) has LiAlH with the ii) middle ketone that obtains according to general method
4Promoted reduction reaction is with the title compound of 95% yield acquisition with the isomer mixture form.By (B.p.=80 ℃/0.008mbar) crude product is carried out purifying of short-path distillation.
Organoleptics property: the smell of wooden, amber.
MS (main isomer): 208 (M+, 2); 190 (35); 175 (51); 121 (100); 107 (20); 105 (17); 93 (16); 91 (14).
1H-NMR:0.85-1.18(m,9H);1.20-2.20(m,13H);3.25-3.60(m,1H);5.10-5.55(m,1H)。
Embodiment 7
Send out preparation of compositions fragrant
By mixing the composition of following ingredients preparation " violet plant " type
Composition
Weight part
Hexyl cinnamic aldehyde 150
Cetalox
1) 20
2-amyl group-1-cyclopentanol
2)30
10%*Farenal
3) 50
Floral
4) 100
Hedione
5) 150
Linalool 200
Mayol
6) 100
Myrrh volatile oil 15
10%* rose oxide compound 40
Red Thymus vulgaris volatile oil 25
Parmantheme
7) 20
900
* in dipropylene glycol
1) 8,12-bis-epoxy-13,14,15,16-tetranorlabdane; Source: Firmenich SA, Geneva Switzerland
2) source: Firmenich SA, Geneva Switzerland
3) source: Haarmann﹠amp; Reimer
4) tetrahydrochysene-2-isobutyl--4-methyl-4 (2H)-Pai Lannuo oil; Source: Firmenich SA, Geneva Switzerland
5) jessamona; Source: Firmenich SA, Geneva Switzerland
6) suitable-7-is to alkanol in the Meng; Source: Firmenich SA, Geneva Switzerland
7) compound spices matrix; Source: Firmenich SA, Geneva Switzerland
Add 2 of 100 weight parts, 2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester makes above-mentioned " violet plant " composition have intension very fine and strong amber/grane ambra, and starting composition is converted into a kind of more comprehensive strong mediation spices.
Embodiment 8
Send out preparation of compositions fragrant
By mixing the composition of following ingredients preparation " wooden amber " type
Composition
Weight part
Acetate Bian ester 70
Oxymethoxyallylbenzene 60
Floral
1) 100
Hedione
2) 60
Iralia?total
3) 180
Phenylethyl alcohol 150
Whitfield's ointment Bian ester 300
Wardia
4) 50
970
* in dipropylene glycol
1) tetrahydrochysene-2-isobutyl--4-methyl-4 (2H)-Pai Lannuo oil; Source: Firmenich SA, Geneva Switzerland
2) jessamona; Source: Firmenich SA, Geneva Switzerland
3) mixture of methyl-jononeionone; Source: Firmenich SA, Geneva Switzerland
4) compound spices matrix; Source: Firmenich SA, Geneva Switzerland
Add 2,2,9 of 30 weight parts, 11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester is enough to make above-mentioned substrate composition to be used for function spices, has the intension of the amber/grane ambra of the consciousness of being highly susceptible to, and increased the functional status of above-mentioned composition.
Embodiment 9
Send out preparation of compositions fragrant
By mixing male sex's perfume substrate composition of following ingredients preparation " wooden-oranges and tangerines " type
Composition
Weight part
Linalyl acetate 400
Citrus bergamia volatile oil 200
8-methoxyl group-2,6,6,8-tetramethyl--3 400
Ring [5.3.1.0 (1,5)] undecane
Citral 20
Geraniol 80
4-cyclohexyl-2-methyl-2-butanols
1)150
Tonka bean camphor 80
Flos Pelargonii volatile oil 30
Hedione
HC
2) 200
Lavandin 200
Lyral?l
3) 250
50%* oak moss 40
Wrinkled Gianthyssop Herb volatile oil 400
Polydantol
4) 50
Salvia japonica Thunb. volatile oil 40
Vanillin 20
Vertofix?coeur
3) 400
Tamarine matrix 41310
5) 40
3000
* in dipropylene glycol
1) source: Firmenich SA, Geneva Switzerland
2) jessamona; Source: Firmenich SA, Geneva Switzerland
3) source: International Flavors﹠amp; Fragrances, USA
4) 3,3-dimethyl-5-(2,2,3-trimethylammonium-3-cyclopentenes-1-yl)-4-penta-2-alcohol; Source: Firmenich SA.Geneva Switzerland
5) compound spices matrix; Source: Firmenich SA, Geneva Switzerland
Add 2,2 of 300 weight parts, 11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-alcohol strengthens and has promoted above-mentioned composition Wrinkled Gianthyssop Herb taste.If replace adding The compounds of this invention with the Wrinkled Gianthyssop Herb volatile oil that adds same amount, then whole fragrance will have less xyloid, mellow and earth smell, with extremely inapparent dense flavor, therefore lose characteristic and quality.
Embodiment 10
Send out preparation of compositions fragrant
By mixing male sex's perfume substrate composition of following ingredients preparation " oranges and tangerines-draft-pungent " type
Composition
Weight part
Geranyl acetate 20
Linalyl acetate 400
10%*4-(4-hydroxyl-1-phenyl)-2-10
Butanone
Citrus bergamia volatile oil 200
Cedroxide
1) 200
Citral 30
Sfuma lemon essential oil 450
4-cyclohexyl-2-methyl-2-butanols
2)90
10%* galbanum volatile oil 70
Lilac compound oil 90
Habanolide
3) 100
HedioneHC
4) 30
Helvetolide
5) 50
Lavender fragrance oil 200
Lyral?l
6) 300
Crystallization moss 20
Semen Myristicae volatile oil 150
Polysantol
7) 60
Suitable-3-Whitfield's ointment hexenol 30
Vertofix?coeur
6) 700
Ylang-ylang extract 100
3300
* in dipropylene glycol
1) trimethylammonium-13-oxygen two ring-[10.1.0]-tridecanes-4, the 8-diene; Source: Firmenich SA, Geneva Switzerland
2) source: Firmenich SA, Geneva Switzerland
3) pentadecenolide; Source: Firmenich SA, Geneva Switzerland
4) jessamona; Source: Firmenich SA, Geneva Switzerland
5) (+)-(1S, 1 ' R)-2-[1-(3 ', 3 '-dimethyl-1 '-cyclohexyl) oxyethyl group]-2-methyl-propyl propionic salt; Source: Firmenich SA, Geneva Switzerland
6) source: International Flavors﹠amp; Fragrances, USA
7) 3,3-dimethyl-5-(2,2,3-trimethylammonium-3-cyclopentenes-1-yl)-4-penta-2-alcohol; Source: Firmenich SA, Geneva Switzerland
Add 2 of 100 weight parts, 2,7,9-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone and regional isomer 2,2 thereof, 8,10-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone gives fine arbor-vitae of above-mentioned composition and fruit intension, and certain is between the taste of the natural oreodaphene of eucalyptus smell and noble quality.Yet described smell intension is compared more true and lasting with the intension that adds above-mentioned natural oil, particularly aftertaste.
Claims (20)
1, a kind of composition contains at least one following formula: compound as fragrant composition
Wherein m represents 0 or 1;
R represents hydrogen atom, or methyl or ethanoyl;
R
1, R
2And R
4Represent hydrogen atom or methyl;
R
3Represent hydrogen atom, or methyl or ethyl; Whole R
1, R
2, R
3And R
42,3 or 4 representatives simultaneously comprise a group of at least one carbon atom; And be under 0 the situation at n, wavy line and the two keys of dotted line representative; Or
Be that wavy line is represented singly-bound under 1 the situation at n; And dotted line is represented singly-bound or two key;
With arbitrary form of its optical isomer or its diastereomer or its mixture, and a spices matrix.
2, composition according to claim 1 is characterized in that, described fragrant composition is a following formula: compound
Wherein n, m, R, R
1, R
3, wavy line and dotted line have with claim 1 in the identical implication that shows.
3, composition according to claim 2 is characterized in that, described fragrant composition is formula (II) compound, wherein m and n and dotted line and wavy line have with claim 2 in identical implication; And
R represents hydrogen atom or ethanoyl;
R
1And R
3Represent hydrogen atom or methyl; Whole R
1And R
32,3 or 4 represent methylidenes simultaneously, and whole R
31,2 or 3 represent methylidenes simultaneously.
4, composition according to claim 2 is characterized in that, described fragrant composition is formula (II) compound, and wherein m has implication identical in the claim 2 with n and dotted line with wavy line; And
R represents hydrogen atom or ethanoyl;
A R
1Be hydrogen atom and another R
1Represent hydrogen atom or methyl;
R
3Represent hydrogen atom or methyl or ethyl; Whole R
1And R
32,3 or 4 for comprising a group of at least one carbon atom, and whole R
3In preferably non-conterminous 1,2 or 3 represent methylidenes or ethyl.
According to the composition of claim 1, it is characterized in that 7, described fragrant composition is a following formula: compound
Wherein R represents hydrogen atom or ethanoyl;
R
1Represent hydrogen atom or methyl; And
R
3Represent hydrogen atom or methyl or ethyl and at least 2 R
3Represent methylidene; And
M be 1 and dotted line represent singly-bound, or
M is 0 and the two keys of dotted line representative.
8, composition according to claim 1 is characterized in that, described composition contains as 2,2 of fragrant composition, 9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester, 2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-alcohol, perhaps by 2,2,7,9-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone and 2,2,8, the mixture that 10-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone is formed.
9, composition according to claim 1 is characterized in that described composition contains as 2,2 of fragrant composition, 11-trimethylammonium spiral shell [5,5] 11 carbon-1-alcohol, 2,2-dimethyl spiral shell [5,5] 11 carbon-8-alkene-1-ketone, (1RS, 6SR, 11SR)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester, (1RS, 6RS, 11RS)-2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-alcohol, (1RS, 6RS, 11RS)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester, 2,6,8-trimethylammonium spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-alcohol, or 7-ethyl-11-methylspiro [5,5] 11 carbon-1-alcohol, or 2,2,10-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-ketone and 2,2,7-trimethylammonium spiral shell [5,5] mixture of 11 carbon-8-alkene-1-ketone, or 6,8-dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-base acetic ester and 7, the mixture of 9-dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-base acetic ester.
10, a kind of composition comprises the same form (I) compound at least, defines as each of claim 1 to 9, and at least one fragrance carrier.
11, a kind of perfuming article contain
I) at least one each defined formula (I) compound as claim 1 to 9; And
An ii) consumer's goods matrix.
12, perfuming article according to claim 11 is characterized in that described consumer's goods matrix is the form with solid or liquid cleaner, textile softener, perfume, Gulong perfume, the liquid that shaves, perfumed soap, body wash or bath salt, mousse, oil or gel, health product, treatment, shampoo, skin care product, reodorant, antiperspirant, air freshener, cosmetic formulations, textiles freshener, Ironing water, paper, rag or SYNTHETIC OPTICAL WHITNER.
13, a kind of give, strengthen, improve or modify send out composition fragrant or the method for the odor property of perfuming article, comprise at least one formula (I) compound that in described composition or article, adds 0.01%~10.0% (weight meter) as claim 1 definition.
14, as formula (I) compound of claim 1 definition, wherein get rid of 2,8-dimethyl spiral shell [5,5] 11 carbon-8-alkene-1-ketone, 2,9-dimethyl spiral shell [5,5] 11 carbon-8-alkene-1-ketone, 1,9-dimethyl spiral shell [5,5] 11 carbon-8-alkene-1-alcohol, 1,8-dimethyl spiral shell [5,5] 11 carbon-8-alkene-1-alcohol, 1,7-dimethyl spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-alcohol, 1,8-dimethyl spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-alcohol, 8,9-dimethyl spiral shell [5,5] 11 carbon-8-alkene-1-ketone and 7,8-dimethyl spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-ketone.
15, the compound as claimed in claim 14 of following formula,
Wherein R represents hydrogen atom or ethanoyl; And
R
3For identical and represent hydrogen atom or R
3For difference and represent hydrogen atom or methyl.
16, the compound as claimed in claim 14 of following formula
2 R wherein
3Represent methylidene and other R
3Represent hydrogen atom.
17, the compound as claimed in claim 14 of following formula
Wherein R represents hydrogen atom or ethanoyl;
R
1Represent hydrogen atom or methyl; And
R
3Represent hydrogen atom or methyl or ethyl and at least 2 R
3Represent methylidene; And
M be 1 and dotted line represent singly-bound, or
M is 0 and the two keys of dotted line representative.
18, compound according to claim 14, wherein compound is: 2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester, 2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-alcohol, 2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-1-alcohol, 2,2-dimethyl spiral shell [5,5] 11 carbon-8-alkene-1-ketone, (1RS, 6SR, 11SR)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester, (1RS, 6RS, 11RS)-2,2,11-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-alcohol, 2,6,8-trimethylammonium spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-alcohol, 7-ethyl-11-methylspiro [5,5] 11 carbon-1-alcohol or (1RS, 6RS, 11RS)-2,2,9,11-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-base acetic ester.
19, a kind of composition contains at least 2 formula (I) compounds as claim 1 definition, wherein gets rid of 2,8-dimethyl spiral shell [5,5] 11 carbon-8-alkene-1-ketone and 2,9-dimethyl spiral shell [5,5] 11 carbon-8-alkene-1-ketone, or 1,9-dimethyl spiral shell [5,5] 11 carbon-8-alkene-1-is pure and mild 1,8-dimethyl spiral shell [5,5] 11 carbon-8-alkene-1-alcohol, or 1,7-dimethyl spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-pure and mild 1,8-dimethyl spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-alcohol.
20, composition according to claim 19, wherein said composition is for containing 2,2,7,9-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone and 2,2,8, the composition of 10-tetramethyl-spiral shell [5,5] 11 carbon-8-alkene-1-ketone, or contain 2,2,10-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-ketone and 2,2, the composition of 7-trimethylammonium spiral shell [5,5] 11 carbon-8-alkene-1-ketone, or contain 6,8-dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-base acetic ester and 7, the composition of 9-dimethyl-spiral shell [4,5] last of the ten Heavenly stems-7-alkene-1-base acetic ester.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
WOPCT/IB02/04217 | 2002-10-14 | ||
IB0204217 | 2002-10-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1496735A CN1496735A (en) | 2004-05-19 |
CN1333059C true CN1333059C (en) | 2007-08-22 |
Family
ID=32040222
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2003101003808A Expired - Lifetime CN1333059C (en) | 2002-10-14 | 2003-10-14 | Spiro-compound used as perfume component |
Country Status (9)
Country | Link |
---|---|
US (1) | US7256170B2 (en) |
EP (1) | EP1411110B1 (en) |
JP (1) | JP4555558B2 (en) |
CN (1) | CN1333059C (en) |
AT (1) | ATE371008T1 (en) |
DE (1) | DE60315776T2 (en) |
ES (1) | ES2290393T3 (en) |
HK (1) | HK1064699A1 (en) |
IL (1) | IL158381A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104837798A (en) * | 2012-12-20 | 2015-08-12 | 弗门尼舍有限公司 | Sage odorant |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6848211B2 (en) * | 2001-05-24 | 2005-02-01 | Regents Of The University Of Minnesota | Cultivated agarwood |
US7378383B2 (en) * | 2004-06-08 | 2008-05-27 | Firmenich Sa | Perfuming ingredients of the woody type |
GB0424643D0 (en) * | 2004-11-09 | 2004-12-08 | Givaudan Sa | Organic compounds |
JP5175272B2 (en) * | 2006-05-22 | 2013-04-03 | フイルメニツヒ ソシエテ アノニム | Patchouli flavoring |
GB2448180A (en) * | 2007-04-05 | 2008-10-08 | Givaudan Sa | Spiro compound and its use in fragrance applications |
CL2008003153A1 (en) * | 2007-10-26 | 2009-07-24 | Japan Tobacco Inc | Spiro-condensed compounds, gpr40 agonists: pharmaceutical composition comprising one of the compounds; and the use of the compounds in the preparation of medications for the treatment of diabetes, hyperglycemia, impaired fasting glucose tolerance, among others. |
EP2424852B1 (en) | 2009-04-29 | 2013-09-18 | Givaudan SA | 2-oxaspiro[5,5]undec-8-ene derivatives useful in fragrance compositions |
WO2012097941A1 (en) * | 2011-01-18 | 2012-07-26 | Firmenich Sa | Spiroepoxy macrocycles as perfuming ingredients |
PL3233780T3 (en) * | 2014-12-19 | 2019-01-31 | Basf Se | 1-(7,10,10-trimethyl-4-bicyclo(6.2.0)decanyl)ethanone as novel aroma chemical |
WO2018155720A1 (en) * | 2017-02-27 | 2018-08-30 | 高砂香料工業株式会社 | Novel spirosesquiterpene compound, flavoring composition and food/drink containing said compound, and method for producing said food/drink |
CN116763963A (en) | 2017-11-22 | 2023-09-19 | 弗门尼舍有限公司 | Spiro compounds as malodor counteracting ingredients |
WO2019101821A2 (en) | 2017-11-22 | 2019-05-31 | Firmenich Sa | Use of volatile compositions to limit or eliminate the perception of malodor |
GB201907995D0 (en) * | 2019-06-05 | 2019-07-17 | Givaudan Sa | Improvements in or relating to organic compounds |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4052457A (en) * | 1974-12-02 | 1977-10-04 | Takasago Perfumery Co., Ltd. | 3,7,11,11-Tetramethyl-spiro-[5,5]undeca-8-ene-1-one |
US4622172A (en) * | 1985-12-06 | 1986-11-11 | International Flavors & Fragrances Inc. | Alkyl-substituted spiroundecenone derivatives, organoleptic utility thereof and processes for preparing same |
US4668432A (en) * | 1986-06-27 | 1987-05-26 | International Flavors & Fragrances Inc. | Alkyl-substituted-oxo-spirodecenene derivatives, organoleptic utility thereof and processes for preparing same |
JPS6425864A (en) * | 1987-03-18 | 1989-01-27 | Tsugio Kisakata | Sauna bath apparatus |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4336197A (en) * | 1980-02-08 | 1982-06-22 | Firmenich Sa | 6-Ethyl-2,10,10-trimethyl-1-oxa-spiro[4.5]deca-3,6-diene |
NL8104271A (en) * | 1981-09-16 | 1983-04-18 | Naarden International Nv | PERFUME COMPOSITIONS AND PERFUMED PRODUCTS CONTAINING SPIROUNDECANONES AND -UNDECENONES AS PERFUME RAW. |
NL8201991A (en) * | 1982-05-13 | 1983-12-01 | Naarden International Nv | PERFUME AND AROMACOMPOSITIONS, PERFUMED ARTICLES AND MATERIALS, AND FOOD AND EDIBLE PREPARATIONS CONTAINING AN OXASPIRODADADATIVATE AS A RAW MATERIAL AND THE OXATOPIEDI4,5. |
US4639330A (en) * | 1986-03-21 | 1987-01-27 | International Flavors & Fragrances Inc. | Alkyl-substituted spirodecenone derivatives, organoleptic utility thereof and processes for preparing same |
JP2526090B2 (en) * | 1988-04-08 | 1996-08-21 | 花王株式会社 | Spiro [4.5] decene derivative, method for producing the same, and perfume composition containing the same |
-
2003
- 2003-09-24 ES ES03021529T patent/ES2290393T3/en not_active Expired - Lifetime
- 2003-09-24 AT AT03021529T patent/ATE371008T1/en not_active IP Right Cessation
- 2003-09-24 DE DE60315776T patent/DE60315776T2/en not_active Expired - Lifetime
- 2003-09-24 EP EP03021529A patent/EP1411110B1/en not_active Expired - Lifetime
- 2003-10-08 US US10/680,138 patent/US7256170B2/en active Active
- 2003-10-13 IL IL158381A patent/IL158381A/en active IP Right Grant
- 2003-10-14 CN CNB2003101003808A patent/CN1333059C/en not_active Expired - Lifetime
- 2003-10-14 JP JP2003354287A patent/JP4555558B2/en not_active Expired - Lifetime
-
2004
- 2004-09-22 HK HK04107298A patent/HK1064699A1/en not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4052457A (en) * | 1974-12-02 | 1977-10-04 | Takasago Perfumery Co., Ltd. | 3,7,11,11-Tetramethyl-spiro-[5,5]undeca-8-ene-1-one |
US4622172A (en) * | 1985-12-06 | 1986-11-11 | International Flavors & Fragrances Inc. | Alkyl-substituted spiroundecenone derivatives, organoleptic utility thereof and processes for preparing same |
US4668432A (en) * | 1986-06-27 | 1987-05-26 | International Flavors & Fragrances Inc. | Alkyl-substituted-oxo-spirodecenene derivatives, organoleptic utility thereof and processes for preparing same |
JPS6425864A (en) * | 1987-03-18 | 1989-01-27 | Tsugio Kisakata | Sauna bath apparatus |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104837798A (en) * | 2012-12-20 | 2015-08-12 | 弗门尼舍有限公司 | Sage odorant |
CN104837798B (en) * | 2012-12-20 | 2017-05-17 | 弗门尼舍有限公司 | Sage odorant |
Also Published As
Publication number | Publication date |
---|---|
JP4555558B2 (en) | 2010-10-06 |
HK1064699A1 (en) | 2005-02-04 |
US7256170B2 (en) | 2007-08-14 |
EP1411110B1 (en) | 2007-08-22 |
ES2290393T3 (en) | 2008-02-16 |
IL158381A (en) | 2007-09-20 |
CN1496735A (en) | 2004-05-19 |
US20040072721A1 (en) | 2004-04-15 |
DE60315776T2 (en) | 2008-06-05 |
JP2004169002A (en) | 2004-06-17 |
ATE371008T1 (en) | 2007-09-15 |
DE60315776D1 (en) | 2007-10-04 |
EP1411110A1 (en) | 2004-04-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1333059C (en) | Spiro-compound used as perfume component | |
MXPA06005893A (en) | Musk odorant compounds. | |
CN101258120B (en) | Alpha-decalones with damascone-woody odor | |
US6184419B1 (en) | α, β-unsaturated ketones | |
CN104046513B (en) | Decenal mixture and use thereof in perfume compositions | |
CN101223123B (en) | Naphthalenone derivative with powdery-ionone type odours | |
CN104003882A (en) | Novel organoleptic compound | |
CN101815696B (en) | Decaline derivatives as perfuming ingredients | |
US4572796A (en) | 1,1,4,7-Tetramethyl-3-indanone, product produced thereby and organoleptic uses thereof | |
CN101861296B (en) | Patchoulol odorant | |
EP2622051B1 (en) | 4,4-dimethyl-decal-1-one or -1-ol derivatives as perfuming ingredients | |
CN104011003A (en) | Woody odorants | |
US6008186A (en) | Perfuming ingredients of woody, fruity odor | |
CN100509749C (en) | Fragrance compound | |
CN101448771A (en) | Patchouli odorant | |
CN1984861A (en) | Citronella and floral perfuming ingredient | |
EP2977365B1 (en) | Novel cyclohexanols and their use in perfume composition | |
JP2021504299A (en) | Amber toning odorant | |
US7838488B2 (en) | Propanol and related compounds and their use in perfume compositions | |
CN104053760B (en) | Cyclododecadienol derivatives as perfuming ingredients | |
EP1063229B1 (en) | Alpha, beta-unsaturated ketones | |
CN104016860A (en) | Novel Organoleptic Compound |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CX01 | Expiry of patent term | ||
CX01 | Expiry of patent term |
Granted publication date: 20070822 |